JP2023041665A - Photosensitive coloring composition, cured film using the same, color filter, optical filter, image display device, solid-state image sensor and infrared sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition which can form a cured film which has the excellent developability, substrate adhesion, pattern shape and solvent resistance after a low-temperature calcination process.

SOLUTION: A photosensitive coloring composition for color filter or optical filter includes: a coloring agent (A); a binder resin (B); a polymerizable compound (C); a photoinitiator (D); an acidic resin type dispersant (ZA); and a leveling agent (E). The binder resin (B) includes an alkali solubile binder resin (Bb) having a constitutional unit having a block isocyanato group in which a blocking agent is diethyl malonate. The binder resin (B) includes the alkali solubile binder resin (Bb) having a constitutional unit having the block isocyanato group. The photoinitiator (D) is a specific O-acyloxime ester-based photoinitiator (D1).

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to photosensitive coloring compositions.

TECHNICAL FIELD The present invention relates to a photosensitive colored composition that is excellent in light utilization efficiency and productivity while having outdoor visibility, and that is advantageous in thinning and flexibility.

2. Description of the Related Art In recent years, as a display element for mobile devices and televisions, an organic EL display element has been attracting attention because it is advantageous in terms of thinness and flexibility in comparison with a conventional liquid crystal display element and has a high light utilization efficiency in principle. An organic EL display element for mobile devices, which is expected to be used outdoors, is equipped with a circularly polarizing plate as an antireflection film in order to prevent deterioration of visibility due to reflection of external light. However, since this circularly polarizing plate cuts not only the outside light but also the light emitted by the organic EL, the light utilization efficiency is greatly reduced. Furthermore, the increase in the thickness of the element is disadvantageous in terms of thinning and flexibility. Therefore, the development of an organic EL display element having good outdoor visibility without using a circularly polarizing plate is progressing. Non-Patent Document 1 and Patent Document 1 disclose a flexible display using a color filter instead of a circularly polarizing plate.

A color filter for suppressing reflection of external light is laminated on a display device in which the above organic EL display elements are laminated. Since the organic light-emitting layer has low heat resistance, it needs to be baked at a low temperature in order to form the colored pixels of the color filter on the organic EL element. Colored pixels of color filters laminated on conventional liquid crystal display elements are baked at a very high temperature of 230.degree. C., but baking at about 70.degree. However, if the baking temperature of the colored pixels is lowered, the curing becomes insufficient, and when the colored pixels are formed in the next step, problems such as peeling of the colored pixels and surface roughness due to the solvent contained in the applied coloring composition occur. . On the other hand, when the exposure dose is increased, the reaction of the crosslinkable component contained in the colored pixels progresses, and although curing progresses, it is extremely difficult to obtain an arbitrary pixel size, and production tact time is increased. is long and unrealistic.

In order to solve the above problems, a composition containing an alkali-soluble resin having a blocked isocyanato group and a reactive diluent (Patent Document 2) and a composition containing a polyfunctional thiol containing a hydroxy group in an alkali-soluble resin having a blocked isocyanato group (Patent Document 3) are disclosed.

However, none of the compositions described in Patent Documents 1 to 3 satisfy all of the developability, substrate adhesion, pattern shape, and solvent resistance after the low-temperature baking step.

Electronic Device Industry Newspaper, April 22, 2021, page 1 Korean Patent Publication No. 10-2013-0134494 International Publication No. 2019/026547 JP 2016-084464 A

An object of the present invention is to provide a photosensitive coloring composition capable of forming a cured film having excellent developability, adhesion to a substrate, pattern shape, and solvent resistance after a low-temperature baking step.

As a result of extensive studies, the present inventors have found that a photosensitive coloring agent containing a dye (A), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a leveling agent (E) The composition, wherein the binder resin (B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, and the photopolymerization initiator (D) is an O-acyl oxime ester-based photopolymerization initiation It has been found that the inclusion of the agent (D1) makes it possible to obtain a photosensitive colored composition capable of forming a cured film having excellent developability, adhesion to a substrate, pattern shape, and solvent resistance after a low-temperature baking step.

That is, the present invention is a photosensitive coloring composition containing a dye (A), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a leveling agent (E), wherein the binder The resin (B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, and the photopolymerization initiator (D) is represented by the following general formula (1), general formula (2), general formula (3) relates to a photosensitive coloring composition characterized by being an O-acyl oxime ester photopolymerization initiator (D1) represented by general formula (4) or general formula (5).

General formula (1):

[In general formula (1), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. indicate. R ³ represents —COR ⁵ , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. ^R5 represents a phenyl group which may have a substituent. R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group, cyclic alkyl group, acyl group and phenyl group of R ¹ to R ⁴ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. may The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with another substituent R ⁶ . ^R6 is a halogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, an acyl group, a nitro group,
A sulfo group and a phenyl group are shown. ]

General formula (2):

[In general formula (2), R ¹ and R ² each independently have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic substituent having 3 to 20 carbon atoms, represents an alkyl group or a phenyl group. R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group or a sulfo group. The alkyl group, cyclic alkyl group, acyl group and phenyl group of R ¹ to R ³ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. may R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the aryl group or arylalkyl group represented by R ⁴ may be further substituted with R ₂₁ , —OR ₂₁ , —COR ₂₁ , hydroxyl group, nitro group, cyano group, halogen atom, or —COOR ₂₁ , R ₂₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group _having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group, A hydrogen atom of the arylalkyl group may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with other substituents. ]

General formula (3):

[In general formula (3), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. indicate. R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. The alkyl group, acyl group and phenyl group of R ¹ to R ³ may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. ^R4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or ^-COR6 . R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. The hydrogen atoms of the substituents in R ¹ to R ⁶ may be further substituted with other substituents. ]

general formula (4)

[In general formula (4), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. indicates R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. ^R4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group optionally interrupted by a hydroxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁵ may be further substituted with other substituents. ]

general formula (5)

[In general formula (5), R ₁ and R ₂ each independently represent R ₁₁ or -COR ₁₁ ,
R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, _an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; The alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl,
R ₃ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and is represented by R ₃ The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl, and the aryl group, arylalkyl group or heterocyclic group represented by _R3 The hydrogen atoms of are further R ₂₁ , —OR ₂₁ , —COR ₂₁ , —SR ₂₁ , —NR ₂₂ R ₂₃ , —CONR ₂₂ R ₂₃ , —NR ₂₂ —OR ₂₃ , —NCOR ₂₂ —OCOR ₂₃ , —NR ₂₂ optionally substituted with COR ₂₁ , —OCOR ₂₁ , —SCOR ₂₁ , —OCSR ₂₁ , —COSR ₂₁ , —CSOR ₂₁ , a hydroxyl group, a nitro group, a cyano group, a halogen atom, or —COOR ₂₁ ;
R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 4 to 20 carbon atoms. The hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ is further a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or may be substituted with a carboxyl group, and the alkylene portion of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ may be -O-, -S-, - adjacent oxygen atoms by COO-, -OCO-, -NR ₂₄ -, -NR ₂₄ CO-, -NR ₂₄ COO-, -OCONR ₂₄ -, -SCO-, -COS-, -OCS- or -CSO-; It may be interrupted 1 to 5 times under no conditions,
R ₂₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, _an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; The alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl,
_R4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom; n represents 0 or 1; ]

The present invention also relates to the photosensitive coloring composition, wherein the leveling agent (E) contains either one of a silicone-based surfactant and a fluorine-based surfactant.

Further, in the present invention, the binder resin (B) is an alkali-soluble binder resin (B1) having a polystyrene-equivalent weight average molecular weight of 5,000 or more and less than 50,000 (however, if the binder resin (Bb) is an alkali-soluble binder resin Except for), it relates to the photosensitive coloring composition.

The present invention also relates to the photosensitive coloring composition, wherein the alkali-soluble binder resin (B1) contains a structural unit (b3) having an alicyclic group.

The present invention also provides the photosensitive coloring composition, wherein the structural unit (b3) having an aliphatic ring group contained in the alkali-soluble binder resin (B1) has a ring represented by formula (b31) or formula (b32). Regarding.

The present invention also relates to the photosensitive coloring composition, wherein the alkali-soluble binder resin (B1) further contains a structure (b1-2) derived from a polybasic acid anhydride.

The present invention also relates to the photosensitive coloring composition, further comprising a resin type dispersant (Z).

The present invention also relates to the photosensitive coloring composition, wherein the resin-type dispersant (Z) contains an acidic resin-type dispersant (ZA).

The present invention also relates to the photosensitive coloring composition, wherein the acidic resin-type dispersant (ZA) contains a photocrosslinkable acidic resin-type dispersant (ZAUV-1).

The present invention also relates to a cured film, which is a cured product of the photosensitive coloring composition.

Moreover, this invention relates to the color filter which has the said cured film.

The present invention also relates to an optical filter having the cured film.

The present invention also relates to an image display device having the cured film.

The present invention also relates to a solid-state imaging device having the cured film.

Moreover, this invention relates to the infrared sensor which has the said cured film.

ADVANTAGE OF THE INVENTION According to said invention, the photosensitive coloring composition which can form the cured film which is excellent in developability, substrate adhesion, pattern shape, and solvent resistance after a low-temperature baking process can be provided. Moreover, the present invention can provide a cured film, a color filter, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor.

FIG. 1 shows a schematic cross-sectional view of an image display device provided with the cured film of the present invention. FIG. 2 shows a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. FIG. 3 shows a schematic cross-sectional view of an infrared sensor provided with the cured film of the present invention.

Hereinafter, the present invention, which will be described in detail with respect to embodiments for carrying out the photosensitive coloring composition of the present invention, is not limited to the following embodiments, and can be carried out by modifying within a range that can solve the problems. .

In the present invention, "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are each 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" . In addition, "C.I." is a color index (C.I.; The Society
of Dyers and Colorists).
A polymerizable unsaturated group is an ethylenically unsaturated double bond. A monomer is an ethylenically unsaturated bond-containing compound that can be polymerized to form a resin. A monomer is an unreacted compound, and a monomer unit is a partial structure forming a resin after polymerization of the monomer.
The molecular weight of the compound in the present invention is a value calculated by calculation, or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for low molecular weight compounds whose molecular weight can be specified, and for compounds having a molecular weight distribution is the polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent.

<Photosensitive coloring composition>
The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a dye (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the binder resin ( B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, and the photopolymerization initiator (D) contains an O-acyloxime ester photopolymerization initiator (D1).

<Dye (A)>
The photosensitive coloring composition of the present invention contains a dye (A). Thereby, the transmittance of each wavelength region can be controlled, and the transmission wavelength of the cured film can be easily controlled. It should be noted that the transmittance may be controlled for areas other than the visible region, and the material may be colorless or transparent as long as the transmittance is controlled.

Pigments, dyes, and near-infrared absorbing dyes may be used as the dye (A), and they can be used in combination.

(pigment)
A pigment is a compound classified as a pigment in the Color Index.
Red pigments include, for example, 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, 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, the pigment described in Patent No. 6368844 is preferable, C. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferred.

Orange pigments include, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35:1,36,36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, pigments described in JP-A-2012-226110, pigments described in JP-A-2017-171915, and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233, pigments described in JP-A-2012-226110, and pigments described in JP-A-2017-171915 are preferred.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred.

Blue pigments include, for example, 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. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

Purple pigments include, for example, 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. Among these, C.I. I. Pigment Violet 19, 23 are preferred.

Specifically, the black pigment is C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. At least two pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and violet pigments may be used as the black colorant.

Among pigments, inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, umber, synthetic iron black, and the like.

(dye)
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Moreover, these derivatives and lake pigments obtained by turning dyes into lakes are also included.

The acid dye preferably has an acidic group such as sulfonic acid or carboxylic acid. Salt-forming compounds, which are salts of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds, are also preferred. A salt-forming compound, which is a salt of a resin component having these functional groups and an acid dye, is also preferred. Moreover, the salt-forming compound is sulfonamidated to be modified into a sulfonic acid amide compound, thereby easily obtaining a photosensitive composition having excellent resistance (light resistance and solvent resistance).
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent resistance (light resistance and solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof is preferred. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance and solvent resistance) and affinity with pigments. In salt-forming compounds of basic dyes, anion components that act as counter ions include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and halogenated carbonization compounds. A salt-forming compound obtained by salt-forming an anion compound having a conjugate base of an organic acid having a hydrogen group and an acid dye is preferred. It should be noted that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Dye structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, metal complex dyes thereof, and the like.

Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, A dye structure derived from a dye selected from quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. A dye structure derived from the selected dye is more preferred.

(Near-infrared absorbing dye)
A near-infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm. A near-infrared absorbing dye is a pigment (also referred to as a near-infrared absorbing pigment) or a dye (also referred to as a near-infrared absorbing dye). Also, a near-infrared absorbing pigment and a near-infrared absorbing dye may be used in combination. From the viewpoint of heat resistance, the near-infrared absorbing pigment is preferably a near-infrared absorbing pigment.

Examples of near-infrared absorbing dyes include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, and croconium compounds. Among these, from the viewpoint of heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds and squarylium compounds are preferred, and naphthalocyanine compounds and squarylium compounds are more preferred.

Cyanine compounds, International Publication WO2006/006573, International Publication WO2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504, etc.; -23868, JP-A-06-192584, JP-A-2000-63691, International Publication WO2014/208514, etc.; JP-A-2009-29955, International Publication WO2018/186490, etc.; Indigo compound, JP-A-2013-230412, etc.; JP-A-2008-88426, etc.; anthraquinone compounds, JP-A-62-903, JP-A-1-172458, etc.; JP-A-2011-068731; the squarylium compound is JP-A-2011-132361, JP-A-2016-142891, WO2017/135359, WO2018/225837, WO2019-001987. No., International Publication No. WO2020/054718, etc.; the croconium compound includes compounds described in International Publication No. WO2019/021767, etc.;

(squarylium compound)
The squarylium compound is preferably a compound represented by the following general formula (10).

general formula (10)

(In general formula (10), R ¹ to R ⁴ are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ¹⁰ , —COR ¹¹ , —COOR ¹² , —OCOR ¹³ , —NR ¹⁴ R ¹⁵ , —NHCOR ¹⁶ , —CONR ¹⁷ R ¹⁸ , —NHCONR ¹⁹ R ²⁰ , —NHCOOR ²¹ , —SR ²² , —SO ₂ R ²³ , —SO ₂ OR ²⁴ , —NHSO ₂ R ²⁵ , —SO ₂ NR ²⁶ R ²⁷ , —B(OR ²⁸ ) ₂ , and —NHBR ²⁹ R ^30. R ¹⁰ to R ³⁰ each independently represent a hydrogen atom, a substituted represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group which may have a group, and when R ¹² of —COOR ¹² is hydrogen (that is, a carboxyl group), hydrogen The atom may be dissociated (i.e., carbonate group) or in the form of a salt, and when R ²⁴ of —SO ₂ OR ²⁴ is a hydrogen atom (i.e., sulfo group), the hydrogen atom may be dissociated. (that is, a sulfonate group), and may be in the form of a salt.In addition, R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring.)

A “substituent” includes, for example, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ¹⁰⁰ , —COR ¹⁰¹ , —COOR ¹⁰² , —OCOR ¹⁰³ , —NR ¹⁰⁴ R ¹⁰⁵ , —NHCOR ¹⁰⁶ , —CONR ¹⁰⁷ R ¹⁰⁸ , —NHCONR ¹⁰⁹ R ¹¹⁰ , —NHCOOR ¹¹¹ , —SR ¹¹² , —SO ₂ R ¹¹³ , —SO ₂ OR ¹¹⁴ , —NHSO ₂ R ¹¹⁵ or —SO ₂ NR ¹¹⁶ R ¹¹⁷ .
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group or an aralkyl group. When R ¹⁰² of —COOR ¹⁰² is hydrogen (ie, carboxyl group), the hydrogen atom may be dissociated (ie, carbonate group), or may be in a salt state. In addition, when R ¹¹⁴ of —SO ₂ OR ¹¹⁴ is a hydrogen atom (ie, sulfo group), the hydrogen atom may be dissociated (ie, sulfonate group) or in a salt state.

Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.
The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-12, even more preferably 1-8. The alkyl group may be linear, branched or cyclic.
The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. Alkenyl groups may be linear, branched or cyclic.
The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 8 carbon atoms. Alkynyl groups may be linear, branched or cyclic.
The number of carbon atoms in the aryl group is preferably 6-25, more preferably 6-15, even more preferably 6-10.
The alkyl portion of the aralkyl group is the same as the alkyl group described above. The aryl portion of the aralkyl group is the same as the above aryl group. The number of carbon atoms in the aralkyl group is preferably 7-40, more preferably 7-30, even more preferably 7-25.
The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1-3. A heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. A heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3-30, more preferably 3-18, even more preferably 3-12.
Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have a substituent or may be unsubstituted. Examples of the substituent include the "substituent" described above.

From the viewpoint of light resistance and heat resistance, the squarylium compound is more preferably a compound represented by the following general formula (11).

general formula (11)

(In general formula (11), R ⁵ to R ⁸ are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, —OR ⁵⁰ , —COR ⁵¹ , —COOR ⁵² , —OCOR ⁵³ , —NR ⁵⁴ R ⁵⁵ , —NHCOR ⁵⁶ , —CONR ⁵⁷ R ⁵⁸ , —NHCONR ⁵⁹ R ⁶⁰ , —NHCOOR ⁶¹ , —SR ⁶² , —SO ₂ R ⁶³ , —SO ₂ OR ⁶⁴ , —NHSO ₂ R ⁶⁵ or —SO ₂ NR ⁶⁶ R ⁶⁷ , —B(OR ⁶⁸ ) ₂ , and —NHBR ⁶⁹ R ^70. R ⁵⁰ to R ⁷⁰ each independently represent a hydrogen atom, a substituted represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group which may have a group, and when R ⁵² of —COOR ⁵² is hydrogen (that is, a carboxyl group), hydrogen The atom may be dissociated (i.e., carbonate group) or in the form of a salt, and when R ⁶⁴ of —SO ₂ OR ⁶⁴ is a hydrogen atom (i.e., sulfo group), the hydrogen atom may be dissociated. (that is, a sulfonate group), and may be in the form of a salt.In addition, R ⁵ and R ⁶ and R ⁷ and R ⁸ may be bonded to each other to form a ring.)

A "substituent" has the same meaning as the above-mentioned "substituent".

Specific examples of the squarylium compound are shown below. In addition, this invention is not limited to these.

(Pyrrolopyrrole compound)
The pyrrolopyrrole compound is preferably a compound represented by the following general formula (12).

general formula (12)

(In general formula (12), R ^1x and R ^1y each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, R ² and R ³ may combine with each other to form a ring, R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR ^4x R ^4y or a metal atom, and R ⁴ is , R ^1x , R ^1y and R ³ , and each R ^4x R ^4y independently represents a substituent. Compounds are described in JP-A-2009-263614, JP-A-2011-68731, and International Publication No. 2015/166873.

R ^1x and R ^1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. In addition, the alkyl group, aryl group and heteroaryl group represented by R ^1x and R ^1y may have a substituent or may be unsubstituted. Examples of substituents include alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, —OCOR ¹¹ , —SOR ¹² , —SO ₂ R ¹³ and the like. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Further, examples of substituents include substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, preferred substituents are alkoxy groups, hydroxy groups, halogen atoms, cyano groups, nitro groups, -OCOR ¹¹ , -SOR ¹² and -SO ₂ R ¹³ . The group represented by R ^1x and R ^1y is preferably an alkoxy group having a branched alkyl group or an aryl group having a group represented by —OCOR ¹¹ as a substituent. The number of carbon atoms in the branched alkyl group is preferably 3 to 30,
3 to 20 are more preferred.

At least one of R ² and R ³ is preferably an electron-withdrawing group, more preferably R ² represents an electron-withdrawing group and R ³ represents a heteroaryl group. A heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a condensed ring, preferably a single ring or a condensed ring with 2 to 8 condensed numbers, more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2. Heteroatoms include, for example, nitrogen atoms, oxygen atoms, and sulfur atoms. Heteroaryl groups preferably have one or more nitrogen atoms. Two R ² groups in general formula (12) may be the same or different. Two R ³ groups in formula (12) may be the same or different.

R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR ^4x R ^4y , and is represented by a hydrogen atom, an alkyl group, an aryl group, or -BR ^4x R ^4y is more preferred, and a group represented by —BR ^4x R ^4y is even more preferred. The substituent represented by R ^4x R ^4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and still more preferably an aryl group. These groups may further have a substituent. Two R ⁴ groups in general formula (12) may be the same or different.

Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. Further, the pyrrolopyrrole compound, paragraphs 0016 to 0058 of JP-A-2009-263614, paragraphs 0037-0052 of JP-A-2011-68731, paragraphs 0014-0027 of JP-A-2014-130343, International Publication No. 2015/166873, paragraphs 0010-0033. In addition, this invention is not limited to these.

(naphthalocyanine compound)
The naphthalocyanine compound is preferably a compound represented by the following general formula (40).

general formula (40)

In formula (40), R ₁ to R ₂₄ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted number of carbon atoms represents an aryl group of 6 to 20, a substituted or unsubstituted heterocyclic group of 4 to 20 carbon atoms, —OR ₂₅ or —SR ₂₆ , wherein R ₂₅ and R ₂₆ are each independently a hydrogen atom, substituted a group-containing or unsubstituted alkyl group having 1 to 20 carbon atoms,
represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms;

Halogen atoms represented by R ₁ to R ₂₄ in formula (40) include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) is not particularly limited as long as it is a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms. The alkyl group may be branched or may form a ring.
Specific examples of the alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso- butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, isohexyl group, sec-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 1-t-butyl-2-methylpropyl group, n-nonyl 3,5,5-trimethylhexyl group, n-decyl group, n-dodecyl group, cyclohexyl group, cyclopentyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group and cyclopentylethyl group.
The alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched chain having 1 carbon atom Alkyl groups from 8 to 8 are more preferred.

The alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have a substituent. Examples of the substituent which may be present include, but are not limited to, an alkoxy group, a halogen group, an amino group, a cyano group, a nitro group and the like.
In the present invention, the phrase "having a substituent" in an alkyl group having 1 to 20 carbon atoms having a substituent means that the saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms has 1 or 2 It means that the above hydrogen atoms are substituted with substituents such as the above-mentioned alkoxy group, halogen group, amino group, cyano group, nitro group, etc. It means that the hydrogen atoms of the saturated aliphatic hydrocarbon group consisting of 20 are not substituted with a substituent such as an alkoxy group, a halogen group, an amino group, a cyano group or a nitro group. In the present invention, hereinafter, "having a substituent" and "unsubstituted" are used in the same meanings as explained here.

The aryl group having 6 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) is particularly limited as long as it is a residue obtained by removing one hydrogen atom from an aromatic ring having 6 to 20 carbon atoms. not to be Specific examples thereof include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group and benzhydryl. groups, trityl groups and pyrenyl groups. A phenyl group is particularly preferred.
The aryl group having 6 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have a substituent. Examples of the substituent which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have.

The heterocyclic group having 4 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) is particularly limited as long as it is a residue obtained by removing one hydrogen atom from a heterocyclic ring having 4 to 20 carbon atoms. not to be Specific examples include a pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, pyrazolyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, indolyl group, isoindolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinolyl group, isoquinolyl group, purinyl group, carbazolyl group, acridinyl group, phenoxazinyl group, phenothiazinyl group and the like. A pyridyl group is particularly preferred.
The heterocyclic group having 4 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have a substituent. Examples of the substituent which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in formula (40) include the same alkyl groups having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40). be done.
The alkyl group having 1 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in formula (40) may have a substituent. Examples of the substituent which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in formula (40) include the same aryl groups having 6 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40). be done.
The aryl group having 6 to 20 carbon atoms represented by R ₂₅ and R ₂₆ in formula (40) may have a substituent. Examples of the substituent which may be present include the same substituents which the alkyl group having 1 to 20 carbon atoms represented by R ₁ to R ₂₄ in formula (40) may have.

R ₁ to R ₂₄ in formula (40) are each independently preferably a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. all of R ₁ to R ₂₄ are hydrogen atoms, or R ₁ , R ₂ to R ₅ , R ₇ , R ₈ to R ₁₁ , R ₁₃ , R ₁₄ to R ₁₇ , R ₁₉ and R ₂₀ to R ₂₃ is a hydrogen atom, and R ₆ , R ₁₂ , R ₁₈ and R ₂₄ are unsubstituted aryl groups having 6 to 20 carbon atoms, or R ₂ to R ₅ , R ₆ , R ₈ to R ₁₁ , R ₁₂ , R ₁₄ to R ₁₇ , R ₁₈ , R ₂₀ to R ₂₃ and R ₂₄ are hydrogen atoms, and R ₁ , R ₇ , R ₁₃ and R ₁₉ are unsubstituted aryl groups having 6 to 20 carbon atoms is more preferable. all of R ₁ to R ₂₄ are hydrogen atoms, or R ₁ , R ₂ to R ₅ , R ₇ , R ₈ to R ₁₁ , R ₁₃ , R ₁₄ to R ₁₇ , R ₁₉ and R ₂₀ to R ₂₃ is a hydrogen atom and R ₆ , R ₁₂ , R ₁₈ and R ₂₄ are phenyl groups, or R ₂ to R ₅ , R ₆ , R ₈ to R ₁₁ , R ₁₂ , R ₁₄ to R ₁₇ , More preferably, R ₁₈ , R ₂₀ to R ₂₃ and R ₂₄ are hydrogen atoms, and R ₁ , R ₇ , R ₁₃ and R ₁₉ are phenyl groups.

In formula (40), M represents two hydrogen atoms, metal atoms, metal oxides or metal halides. When M represents two hydrogen atoms, structures are formed in which the NMN portion in formula (40) is shown as two NH.
Metal atoms represented by M in formula (40) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium and tin.
Examples of metal oxides represented by M in formula (40) include titanyl and vanadyl.
Examples of metal halides represented by M in formula (40) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride and silicon chloride.
M in formula (1) is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride or tin(II) chloride, more preferably copper, zinc, vanadyl or titanyl. , vanadyl.

Next, a method for producing the compound represented by formula (40) will be described. The method for producing the compound represented by formula (40) is not particularly limited, and conventionally known methods can be appropriately used. For example, a method of synthesizing a naphthalocyanine having a metal at the center from a corresponding naphthalenedicarboxylic acid or its derivative (acid anhydride, diamide, dinitrile, etc.) by direct cyclization in the presence of a metal compound is known (e.g. , Chemistry-A European Journal, Vol. 9, pp. 5123-5134 (published 2003)). At this time, it is preferable to coexist with a catalyst (for example, ammonium molybdate) and urea. Alternatively, after synthesizing a metal-free naphthalocyanine using a lithium compound, it can be synthesized using a metal compound as described later.

Although the cyclization reaction can be carried out without a solvent, it is preferably carried out in an organic solvent. The organic solvent that can be used in the cyclization reaction is not particularly limited as long as it has low reactivity with naphthalenedicarboxylic acid or a derivative thereof as a starting material, but an inert solvent that does not exhibit reactivity is preferred. organic solvents such as inert solvents such as benzene, toluene, xylene, nitrobenzene, monochlorobenzene, o-chlorotoluene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; methanol , ethanol, 1-propanol, 2-propanol,
alcohols such as 1-butanol, 1-hexanol, 1-pentanol and 1-octanol; pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, N,N-dimethylacetophenone , triethylamine, tri-n-butylamine, dimethylsulfoxide and sulfolane, and other aprotic polar solvents. Among these, 1-chloronaphthalene, 1-methylnaphthalene, 1-octanol, dichlorobenzene, benzonitrile and sulfolane are preferred, and 1-octanol, dichlorobenzene, benzonitrile and sulfolane are more preferred. One of these solvents may be used alone, or two or more thereof may be used in combination.

The amounts of the naphthalene dicarboxylic acid or its derivative and the metal compound used in the cyclization reaction are not particularly limited as long as the reaction proceeds. For example, the naphthalene A dicarboxylic acid or a derivative thereof is used in an amount of usually 1 to 500 parts by mass, preferably 10 to 350 parts by mass, and a metal compound is usually used in an amount of 0.25 to 0.5 parts per mol of the naphthalenedicarboxylic acid or derivative thereof. mol, preferably in the range of 0.25 to 0.4 mol. The conditions for the cyclization reaction are also not particularly limited, but the reaction temperature is preferably in the range of 30 to 250°C, more preferably in the range of 80 to 200°C. The reaction time is preferably 1 to 30 hours. Moreover, the cyclization reaction may be carried out in an air atmosphere, but is preferably carried out in an inert gas atmosphere (for example, under circulation of nitrogen gas, helium gas, argon gas, etc.).

When synthesizing the compound represented by the formula (40) using the metal-free naphthalocyanine and the metal compound, the ratio of the raw materials used is 0.1 of the metal compound per 1 mol of the metal-free naphthalocyanine. It is preferably used in an amount of from 1 to 10 mol, more preferably from 0.5 to 5 mol, even more preferably from 1 to 3 mol. As metal compounds, inorganic and organic metal compounds can be used, and specific examples thereof include halides (eg, chlorides, bromides), sulfates, acetates, metal acetylacetonates, and the like. Halides and acetates are preferred, and halides are more preferred.
The compound obtained by the above reaction may be subjected to crystallization, filtration, washing, drying, etc. according to conventionally known methods.
By such operation, the naphthalocyanine compound represented by the formula (40) can be efficiently obtained with high purity.

Specific examples of the compound represented by Formula (40) are shown below, but the present invention is not limited thereto.

The naphthalocyanine compounds represented by formula (40) can be used singly or in combination.
The naphthalocyanine compound represented by formula (40) preferably has a maximum absorption wavelength in the wavelength range of 750 to 1500 nm, more preferably in the wavelength range of 780 to 1000 nm.

Moreover, the naphthalocyanine compound is preferably a compound represented by the following general formula (13).

general formula (13)

(In general formula (13), R ¹ to R ²⁴ are each independently a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, or a substituted optionally substituted aryl group, optionally substituted cycloalkyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted alkylthio an optionally substituted arylthio group, an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group show.
Z is a polymer moiety containing a monomer unit represented by general formula (14) or a phosphorus compound moiety represented by general formula (15). )

(In general formula (14), X is -CONH-R ²⁵ -, -COO-R ²⁶ -, -CONH-R ²⁷ -O-, -COO-R ²⁸ -O-, and R ²⁵ to R ²⁸ are R ³¹ represents an alkylene group or an arylene group optionally linked by —O—, —CO—, —COO—, —OCO—, —CONH—, or —NHCO— between carbon atoms. represents hydrogen or a methyl group, n is an integer of 0 or 1 to 10, * is a bond with Al.)
(In general formula (15), R ²⁹ and R ³⁰ are each independently a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted represents a good alkoxyl group or an aryloxy group which may have a substituent, and R ²⁹ and R ³⁰ may combine with each other to form a ring.* is a bond with Al.)

Specific examples of the compound represented by formula (13) are shown below. In addition, this invention is not limited to these.

A near-infrared absorption dye can be used individually or in combination of 2 or more types. When two or more types are used in combination, it is preferable to use at least two types of compounds having different maximum absorption wavelengths. As a result, compared with the case of using one type of near-infrared absorbing dye, the waveform of the absorption spectrum is broadened, and near-infrared rays in a wide wavelength range can be absorbed.

Dye (A) can be used alone or in combination of two or more.

The content of the dye (A) is preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass, based on 100% by mass of non-volatile matter in the photosensitive coloring composition.

(Refinement of pigment)
It is preferable to use the pigment after miniaturization. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution-precipitation can be used. Among these, the salt milling treatment by the kneader method, which is one type of wet grinding, is preferable. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm.
From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferred from the viewpoint of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment 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 amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

If necessary, a resin may be added to the salt milling treatment. The type of the resin is not particularly limited, and includes natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. Among these, it is preferable that they are solid at room temperature, insoluble in water, and partially soluble in the above organic solvents. The amount of the resin to be added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.
(removal of metal)
If a large amount of the specific metal element exists in the coloring composition as an impurity other than the constituent components of the pigment, the dispersion stability over time is hindered, and the heat resistance may be lowered, or the sensitivity may be lowered. In addition, a color filter produced using this may have foreign matter, which tends to result in a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is preferably 500 mass ppm or less.

The total amount of specific metal elements contained in the photosensitive coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more. If it is within the above range, it is possible to obtain a photosensitive coloring composition capable of suppressing the cost, excellent in storage stability, and capable of forming a color filter with little generation of foreign matter and reduction in brightness.

The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, more preferably 50 mass ppm or less.

In addition, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that make up the pigment should also contain few impurities that do not function effectively. I can. Further, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc. mixed with materials (for example, catalysts) used in the manufacturing process of various raw materials of the photosensitive coloring composition are also low.

As a method for removing the dye (A) or the mixed metal from the equipment in the manufacturing process, JP 2010-83997, JP 2018-36521, JP 7-198928, JP 8-333521 Japanese Patent Laid-Open No. 2009-7432, etc., and a method of removing magnetic foreign matter using a magnet, etc., described in Japanese Patent Laid-Open No. 2011-48736.

The content of the specific metal element can be measured by inductively coupled plasma atomic emission spectrometry (ICP).
<Dye derivative>
A dye derivative can be optionally used in the coloring composition, particularly when the dye (A) is a pigment. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, benzoiso Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives are disclosed in JP-A-2007-226161, WO2016/163351, JP-A-2017-165820, and Japanese Patent No. 5753266. Anthraquinone-based dye derivatives are disclosed in JP-A-63-264674 and JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-1813
83 and JP-A-2005-213404. 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, and even more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment.

By adding a pigment derivative to the pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the surface of the pigment. In comparison, the primary particles of the pigment can be made finer.

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 surface of the pigment, and the surface of the pigment becomes polar and adsorbs the resin-type dispersant. is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time when used as a colored composition or colored curable composition are improved. do. In addition, by improving the compatibility, the coating film has excellent temporal stability when the colored curable composition is applied to a glass substrate or the like, and the waiting time from application of the colored curable composition to exposure (PCD: Post
Coating Delay), the waiting time from exposure to heat treatment (PED: Post Exposure Delay), stability and characteristic dependence 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 (Z)>
A known resin-type dispersant (Z) can be used in the photosensitive coloring composition of the present invention.
As is well known, the resin-type dispersant (Z) is used in the production of a pigment dispersion, which is a precursor of a photosensitive coloring composition, and is distinguished from the binder resin by being adsorbed on the surface of the pigment.
The resin-type dispersant has a dye affinity site having a property of adsorbing to the dye (A) and a site compatible with the binder resin, and adsorbs to the dye (A) to disperse in the binder resin. Anything can be used as long as it has a stabilizing function. Specifically, 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, modified products thereof, poly(lower alkyleneimine) and free carboxyl groups Oil-based dispersants such as amides and their salts formed by reaction with polyesters, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid Water-soluble resins such as copolymers, polyvinyl alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphate esters, etc. are used. They can be used singly or in combination of two or more.

(Acidic resin-type dispersant (ZA))
Preferred examples of the acidic resin-type dispersant (ZA) include resin-type dispersants having an aromatic carboxylic acid structure, which are disclosed in WO2008/007776, JP-A-2008-029901, and JP-A-2009-155406. JP, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, JP 1996-143651, etc. manufactured by known methods be able to.

(Basic resin-type dispersant (ZB))
Preferable examples of the basic resin-type dispersant (ZB) include nitrogen atom-containing graft copolymers, and nitrogen atoms having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include atom-containing acrylic block copolymers and urethane polymer dispersants.

Further, as disclosed in JP-A-2009-185277, a resin-type dispersant having an aromatic carboxyl group and a vinyl-based resin having a tertiary amino group (having the function of a resin-type dispersant) are combined. Combination use is also mentioned as a preferable example.

The resin-type dispersant (Z) is preferably used in an amount of about 3 to 200% by mass, more preferably in an amount of about 5 to 100% by mass, based on the total amount of the dye (A).

(Photocrosslinkable acidic resin-type dispersant (ZAUV-1)))
The photocrosslinkable acidic resin-type dispersant (ZAUV-1) is a dispersant having an aromatic carboxylic acid structure and a vinyl polymer moiety having a (meth)acryloyl group. The photocrosslinkable acidic resin-type dispersant (ZAUV-1) is, for example, (1) an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, and separately A method of synthesizing by reacting hydroxyl groups in the synthesized vinyl polymer. (2) a method of reacting an acid anhydride group in the acid anhydride with a hydroxyl group-containing thiol and then polymerizing a monomer starting from the thiol group of the thiol to form a vinyl polymer moiety; mentioned. The photocrosslinkable acidic resin-type dispersant (ZAUV-1) is, in other words, a dispersant composed of a polyester portion having a carboxyl group and a vinyl polymer portion B obtained by polymerizing a monomer. It is a dispersant having an acryloyl group. Photocrosslinkable acidic resin-type dispersants (ZAUV-1) include, for example, comb-type dispersants described in JP-A-2011-157416.

Tetracarboxylic dianhydrides are, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6 -tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, aliphatic tetracarboxylic dianhydride such as bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyro Melitic dianhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 3,3′,4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 3,3′,4,4′-Biphenylethertetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3′,4,4′ -tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4, 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'- Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4 '-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl ) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or aromatic tetracarboxylic dianhydride such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride; . Among these, aromatic tetracarboxylic dianhydrides are preferable, and tetracarboxylic dianhydrides having two or more aromatic rings are more preferable in view of excellent adsorption to the colorant.

Tricarboxylic anhydrides include, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride etc.), 3,4,4′-benzophenonetricarboxylic anhydride, 3,4,4′-biphenylethertricarboxylic anhydride, 3,4,4′-biphenyltricarboxylic anhydride, 2,3,2′- biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4,4'-biphenylsulfonetricarboxylic anhydride and the like. Among these, trimellitic anhydride is more preferable.

((Meth)acryloyl group-containing vinyl polymer moiety)
The (meth)acryloyl group-containing vinyl polymer moiety can be synthesized by reacting the hydroxyl group of the vinyl polymer moiety with the isocyanate group in the isocyanate group-containing monomer. As a result, photocurability is obtained at the vinyl polymer site which is the relaxation site.

Examples of isocyanate group-containing monomers include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate and the like.

The hydroxyl-containing thiol is preferably a compound having two hydroxyl groups and one thiol group. As such, hydroxyl group-containing thiols include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2- mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

The monomer used for synthesizing the vinyl polymer moiety includes, for example, at least one thermally crosslinkable functional group selected from the group consisting of hydroxyl group, oxetane group, t-butyl group and blocked isocyanato group, carboxyl group-containing monomer, mers and other monomers.

Hydroxyl-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono hydroxyalkyl (meth)acrylates such as (meth)acrylates and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
Examples of (meth)acrylamide-based monomers having a hydroxyl group include N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl) ( N-(hydroxyalkyl)(meth)acrylamides such as meth)acrylamide;
Vinyl ether monomers having a hydroxyl group, such as hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, 2-(or 3- or 4-) hydroxybutyl vinyl ether;
As allyl ether monomers having a hydroxyl group, hydroxyalkyls such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3- or 4-) hydroxybutyl allyl ether Allyl ethers are mentioned.

Examples of the oxetane group-containing monomer include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl]alkyloxetane and the like. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred.

Examples of monomers having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

Block isocyanato group-containing monomers include, for example, 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. are mentioned.

The amount of the thermally crosslinkable functional group-containing monomer used is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the total amount of monomers. When used in an appropriate amount, the solvent resistance of the film is further improved.

Carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Among these, (meth)acrylic acid is preferred.

Other monomers include (meth)acrylic acid esters, nitrogen-containing group monomers, and vinyl monomers. (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, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate and other (meth)acrylic acid alkyl esters; cyclohexyl (meth)acrylate, tertiarybutylcyclohexyl (meth)acrylate, Alicyclic (meth)acrylates such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ) acrylates, aromatic (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate, and 3-methyl-3-oxetanyl (meth)acrylate; Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;

Nitrogen-containing group monomers include, for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, N-substituted (meth)acrylamides such as acryloylmorpholine; amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; meth)acrylonitrile, etc. Nitriles of.

Vinyl monomers include, for example, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Examples include fatty acid vinyls.

(Non-photocrosslinkable acidic resin type dispersant (ZA-2))
The resin-type dispersant (Z) can be used in combination with a non-photocrosslinkable acidic resin-type dispersant (ZA-2). The resin-type dispersant (ZA-2) is a dispersant that has an aromatic carboxylic acid structure and a vinyl polymer moiety that does not have a (meth)acryloyl group. The resin-type dispersant (ZA-2) has a structure obtained by removing the (meth)acryloyl group from the structure of the resin-type dispersant (ZAUV-1). Resin-type dispersants (ZA-2) include, for example, comb-type dispersants described in Japanese Patent No. 4,396,777 and Japanese Patent No. 5,181,664. By using both the resin type dispersant (ZAUV-1) and the resin type dispersant (ZA-2), the photocurability of the film can be appropriately adjusted.

(Other resin-type dispersants)
The resin-type dispersant (Z) can be used in combination with dispersants other than those described above.
Other dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups and its salts, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl Water-soluble resins such as pyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters and the like can be mentioned.

The resin type dispersant (Z) can be used alone or in combination of two or more.

The amount of the resin type dispersant (Z) used is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the dye (A). When used in an appropriate amount, the film formability is further improved.

[Binder resin (B)]
The photosensitive coloring composition of the present invention contains a binder resin (B), an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group as an essential component, and an alkali-soluble binder resin (B1) (however, , except for the binder resin (Bb)).

(Alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group)
The photosensitive coloring composition of the present invention contains, as a binder resin (B), an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group as an essential component.
As a result, a cured film having good developability, substrate adhesion, pattern shape, and solvent resistance after the low-temperature baking step can be obtained.

(Structural unit (Bb-1) having a blocked isocyanato group)
The structural unit (Bb-1) having a blocked isocyanato group contained in the alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group is a structural unit derived from a monomer containing a blocked isocyanato group. Examples of the monomer include monomers having an ethylenically unsaturated bond and a blocked isocyanato group, such as isocyanate compounds having a vinyl group, (meth)acryloyloxy group, etc. in the molecule, and blocking the isocyanato group with a blocking agent. compounds that have The reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. When using a solvent, it is necessary to use a solvent that is inert to the blocked isocyanato groups. In the blocking reaction, an organic metal salt such as tin, zinc or lead, or a tertiary amine may be used as a catalyst. The reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C. Examples of the isocyanate compound include compounds represented by the following formula (20).

formula (20)

In the above formula (20), R ¹ represents a hydrogen atom or a methyl group, R ² represents -CO-, -COOR ³ - (wherein R 3 is an alkylene group having 1 to 6 carbon atoms) or -COO- ^R4O-
CONH--R ⁵ -- (wherein R ⁴ is an alkylene group having 2 to 6 carbon atoms, and R 5 is an alkylene group having 2 to 12 carbon atoms which may have a substituent or an alkylene group having 6 to 6 carbon atoms. is an arylene group of 12). R2 is preferably ^-COOR3- , where ^R3 is preferably an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the above formula (20) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2 -isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate and the like. An equimolar (1 mol:1 mol) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. The alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3 -isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate and the like.

Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate and methacryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred. more preferred.

In the present invention, the notation of (meth)acrylate means that either acrylate or methacrylate may be used, and the notation of (meth)acrylic acid may be either acrylic acid or methacrylic acid. means.

Examples of blocking agents for blocking isocyanato groups in the isocyanate compounds include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; methanol, ethanol, propanol, butanol,
Alcohols such as ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol; phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o- Butylphenol such as isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitro Phenolics such as phenol and p-chlorophenol; Active methylenes such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone;
mercaptans such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan;
Amines such as diphenylamine, phenylnaphthylamine, aniline, carbazole;
acid amides such as acetanilide, acetanisidide, acetic acid amide, benzamide;
acid imides such as succinimide and maleimide;
imidazole, such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazole, such as pyrazole and 3,5-dimethylpyrazole;
Urea series such as urea, thiourea, ethylene urea;
carbamates such as phenyl N-phenylcarbamate and 2-oxazolidone; imines such as ethyleneimine and polyethyleneimine;
oximes such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime, cyclohexanone oxime;
Bisulfites such as sodium bisulfite and potassium bisulfite are included. These blocking agents may be used alone or in combination of two or more.

The blocking agent protects the highly reactive isocyanato groups, but the blocked isocyanato groups are dissociated by heating to regenerate the isocyanato groups. In the present invention, the isocyanato group is a reactive functional group contained in the resin-type dispersant (Z), the binder resin (B), and the polymerizable compound (C), that is, an acid group or a hydroxy group optionally contained, It reacts with amino groups and the like to form a cured product with a high cross-linking density.

From the viewpoint of low-temperature curability and storage stability of the photosensitive resin composition described below, a blocked isocyanato group-containing (meth)acrylate is used as the monomer that provides the structural unit (Bb-1) having a blocked isocyanato group. is preferred. The dissociation rate of the blocked isocyanato group when heat-treated at 100° C. for 30 minutes is preferably 5 to 99 mass %, more preferably 8.
It is preferred to use blocked isocyanato group-containing (meth)acrylates of up to 97% by weight, most preferably from 10 to 95% by weight. The dissociation rate of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate was obtained by preparing an n-octanol solution having a concentration of 20% by mass of the blocked isocyanato group-containing (meth)acrylate, and adding 1 Dibutyltin laurate equivalent to % by mass and phenothiazine equivalent to 3% by mass (polymerization inhibitor)
was added, followed by heating at 100°C for 30 minutes. By using a blocked isocyanato group-containing (meth)acrylate having a dissociation rate in the above range, the stability of the copolymer during synthesis can be sufficiently ensured, and the baking temperature during the preparation of the cured coating film can be sufficiently increased. can be lowered, and the solvent resistance of the cured coating film can be sufficiently ensured. Blocking agents for blocked isocyanato group-containing (meth)acrylates having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethylketoxime, 3,5 - dimethylpyrazole and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole and methyl ethyl ketoxime are more preferable from the viewpoint of low-temperature curability.

It is also preferable to use a blocked isocyanato group-containing (meth)acrylate whose dissociation temperature of the blocked isocyanato group is 80° C. or higher. When a blocked isocyanato group-containing (meth)acrylate having a dissociation temperature of 80° C. or higher is used, the stability of the copolymer during synthesis can be sufficiently ensured, and unintended cross-linking can be prevented during the modification reaction described below. Reaction can be reduced. On the other hand, when the dissociation temperature of the blocked isocyanato group is 160° C. or less, the baking temperature can be sufficiently lowered and the solvent resistance of the cured coating film can be sufficiently secured. The dissociation temperature of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate was determined by preparing an n-octanol solution having a concentration of 20% by mass of the blocked isocyanato group-containing (meth)acrylate, and adding 1 After adding dibutyltin laurate equivalent to 3% by mass and phenothiazine (polymerization inhibitor) equivalent to 3% by mass, heating at a predetermined temperature for 30 minutes, the mass reduction rate of the blocked isocyanato group-containing (meth)acrylate was measured by HPLC analysis, and the mass reduction rate was 80% by mass
The temperature above is defined as the dissociation temperature of the blocked isocyanato group.

Examples of the blocked isocyanato group-containing (meth)acrylate include Karenz (registered trademark) MOI-DEM (a reaction product of methacryloyloxyethyl isocyanate and diethyl malonate) represented by the following formula (2), Showa Denko K.K. company, dissociation temperature of blocked isocyanato group: 90°C, dissociation rate: 90% by mass), Karenz MOI-BP (reaction of methacryloyloxyethyl isocyanate and 3,5-dimethylpyrazole) represented by the following formula (3) Product, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanato group: 110° C., dissociation rate: 70% by mass), Karenz MOI-BM represented by the following formula (4) (metacroyloxyethyl isocyanate and methyl ethyl ketoxime , dissociation temperature of blocked isocyanato group: 130°C, dissociation rate: 18% by mass, manufactured by Showa Denko K.K.) and acrylates corresponding to these. These blocked isocyanato group-containing (meth)acrylates may be used alone or in combination of two or more.

Equation (21)

Equation (22)

Equation (23)

The ratio of the structural unit (Bb-1) having a blocked isocyanato group contained in the binder resin (B) is not particularly limited, but is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, most preferably is 3 to 25 mol %. When the proportion of the structural unit (Bb-1) having a blocked isocyanato group is 1 to 40 mol%, the solvent resistance of the cured coating film is improved and the storage stability of the binder resin (B) is maintained.

(Alkali-soluble binder resin (B1))
The alkali-soluble binder resin (B1) may be any resin that dissolves in an alkali developer, and known resins can be used.

The alkali-soluble binder resin (B1) preferably contains a structural unit (b3) having an aliphatic ring group from the viewpoint of development stains and solvent resistance, and contains a ring represented by formula (b31) or formula (b32). is more preferred.

The glass transition temperature of the alkali-soluble binder resin (B1) is preferably -50 to 150°C, more preferably -10 to 150°C, and further preferably -10 to 80°C, from the viewpoint of development stains, solvent resistance, and development speed. preferable.

As the glass transition temperature (hereinafter also referred to as Tg), a measured Tg obtained by actual measurement can be applied. Specifically, the measured Tg can use a value measured by differential scanning calorimetry (DSC).
However, if measurement is difficult due to decomposition of the resin, etc., the calculated Tg obtained by the following formula is applied.
1/Tg= _W1 / _Tg1 + _W2 / _Tg2 +...+ _Wn / _Tgn
Here, the resin to be calculated is assumed to be a copolymer of n kinds of monomer components from W ₁ to W _n , W _n is the weight fraction of the n-th monomer, Tg _n is n is the glass transition temperature (absolute temperature) of the homopolymer of the first monomer. The value of the glass transition temperature of a homopolymer (hereinafter also referred to as a homopolymer) of each monomer is described in Brandrup, J.; Immergut, E.; H. The values given in the ed. "Polymer Handbook, Third edition, John wiley & sons, 1989" are used.

The alkali-soluble binder resin (B1) preferably has a (meth)acryloyl group from the viewpoint of developability and substrate adhesion. For example, a (meth)acryloyl group can use a structural unit (b1-1) derived from an epoxy group-containing monomer. 2 to 90 mol% of the structural unit (b1-1) derived from an epoxy group-containing monomer, 2 to 80 mol% of the aromatic ring-containing structural unit (b2) in all structural units, an aliphatic ring It is preferable to contain the contained structural unit (b3) in an amount of 2 to 80 mol % of all structural units. The structural unit derived from the epoxy group-containing monomer is a structural unit obtained by reacting an epoxy group in the epoxy group-containing monomer with a carboxyl group.

Methods for adding (meth)acryloyl groups to the alkali-soluble binder resin (B1) include, for example, the following methods (i) to (iii).

<Method (i)>
There is a method (i) of adding a carboxyl group of a carboxyl group-containing monomer to the epoxy group of the epoxy group-containing monomer contained in the alkali-soluble binder resin (B1).

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidiether, 3,4-epoxybutyl (meth)acrylate, 3-methyl- 3,4-epoxybutyl (meth)acrylate, 3-ethyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxy Hexyl (meth)acrylate, α-ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso)crotonate glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, N-(3,5) -dimethyl-4-glycidyl)benzyl acrylamide, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyl Oxymethylstyrene, 2
,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4 , 6-triglycidyloxymethylstyrene. From the viewpoint of easy availability of industrial products, glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether represented by the following general formula (3) are preferable, and the concentration of ethylenically unsaturated groups is increased. Glycidyl (meth)acrylate is more preferable in that UV curing in the coating film formed from the photosensitive coloring composition can easily proceed.

General formula (16):

(In general formula (16), R ⁶ is a hydrogen atom or a methyl group, l is an integer of 0 or 1.)

Carboxyl group-containing monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among these, acrylic acid and methacrylic acid are preferred.

The site obtained by adding the carboxyl group of the carboxyl group-containing monomer to the epoxy group of the epoxy group-containing monomer is synthesized, and the site obtained by reacting the polybasic acid anhydride is derived from the polybasic acid anhydride. It is called a structural unit (b1-2). From the viewpoint of developability, the structural unit (b1-2) is preferable as the structural unit (b1-1) derived from the epoxy group-containing monomer.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[Structural Unit (b1-1) Derived from Epoxy Group-Containing Monomer]
The content of the structural unit (b1-1) derived from the epoxy group-containing monomer is, from the viewpoint of development resistance and substrate adhesion, the molar ratio of the total structural units of the alkali-soluble binder resin (B1) to the solvent shock. From the viewpoint of durability and developability, it is preferably 2 to 90 mol %. From the viewpoint of heat resistance, the double bond equivalent is preferably adjusted to 200-1200, more preferably 200-800, and even more preferably 200-700.
The double bond equivalent is the weight per mole of the ethylenically unsaturated double bond of the resin, and can be calculated by the following formula.
Double bond equivalent = weight of resin (g) / amount of ethylenically unsaturated double bonds in resin (mol)

<Method (ii)>
A method (ii) of adding an epoxy group of an epoxy group-containing monomer to the carboxyl group of the carboxyl group-containing structural unit (b4) contained in the alkali-soluble binder resin (B1) can be mentioned.

<Method (iii)>
For example, the method (iii) of reacting the isocyanate group of the isocyanate group-containing monomer with the hydroxyl group of the hydroxyl group-containing monomer unit contained in the alkali-soluble binder resin (B1) can be mentioned.

Hydroxyl group-containing monomers, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) Examples include acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate.

Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

The epoxy group-containing monomer may be used as a copolymerization component in the step of forming the binder resin (B), or may be introduced into the binder resin through addition reaction with the carboxyl groups of the binder resin. A hydroxyl group produced by an addition reaction with an epoxy group or a carboxyl group contributes to the dispersion stability of the pigment and enhances the solvent shock resistance.

[Structural Unit (b2) Having an Aromatic Ring Group]
The structural unit (b2) having an aromatic ring group has a cyclic structure with an aromatic ring group represented by general formula (17) or general formula (18) and functions as an affinity site for the dye (A) or dye derivative. do. The content of the structural unit (b2) having an aromatic ring group is preferably 2 to 80 mol% of the total structural units of the binder resin (B). This improves developability and further suppresses solvent shock.

[In general formulas (17) and (18), R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. The dashed line in general formula (18) indicates a cyclic structure containing one or more saturated or unsaturated heterocyclic rings which may have a substituent, adjacent to the benzene ring. ]

Monomers constituting the structural unit (b2) having an aromatic ring group include styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, and bisphenol A diglycidyl ether di(meth)acrylate. , monomers and oligomers such as (meth)acrylic acid esters of methylolated melamine, and monomers represented by general formula (19).

general formula (19)

[In the general formula (19), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ is a carbon optionally having a benzene ring It is an alkyl group of numbers 1-20, and n is an integer of 1-15. ]

The monomer represented by the general formula (19) is, for example, New Frontier CEA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. [EO-modified cresol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : methyl group, n=1 or 2,], NP-2 [n-nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n=2], N-177
E [n-nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n=16 to 17], or PHE [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1],
Daicel Corporation, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ¹
: hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], or Ebecryl110 [ethoxylated phenyl acrylate (EO2 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=2], Toagosei Aronix M-101A [phenol EO-modified (n≈2) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈2], M-102 [phenol EO-modified (n≈4) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈4], M-110 [paracumylphenol EO-modified (n≈1) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : paracumyl, n≈1], M-111 [n-nonylphenol EO-modified (n≈1) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n ≈4], or M-117 [n-nonylphenol PO-modified (n≈2.5) acrylate, R ¹ : hydrogen atom, R ² : propylene group, R ³ : n-nonyl group, n≈2.5], Kyoei Co., Ltd. Light acrylate PO-A [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], P-200A [phenoxypolyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈2], NP-4EA [nonylphenol EO adduct acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n≈4 ], or NP-8EA [[nonylphenol EO adduct acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ¹ : methyl group, R ² : propylene group, R ³ : hydrogen atom, n=1], BLEMMER ANE-300 manufactured by NOF Corporation [nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group, n≈5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R ¹ : hydrogen atom, R ² : propylene group, R ³ : n-nonyl group, n≈5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : ethylene group and propylene group, R ³ : n -nonyl group, n≈5+5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : ethylene group and propylene group, R ³ : n-nonyl group, n≈9+3 ], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : ethylene group and propylene group, R ³ : n-nonyl group, n≈5+2], AAE-50 [phenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], AAE-300 [phenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ¹ : methyl group, R ² : ethylene group, R ³ : hydrogen atom, n=1], PAE-100 [phenoxypolyethylene glycol methacrylate, R ¹ : methyl group, R ² : ethylene group, R ³ : hydrogen atom, n=2] or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ¹ : methyl group, R ² : ethylene group and propylene group, R ³ : hydrogen atom, n≈6+6], Shin-Nakamura Chemical NKESTER AMP-10G [phenoxyethylene glycol acrylate (EO 1 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], AMP-20G [phenoxyethylene glycol acrylate (EO2 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ¹ : methyl group, R ² : ethylene group , R ³ : hydrogen atom, n=1 ], Osaka Organic Chemical Co., Ltd. Viscoat #192 [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], or Nippon Kayaku SR-339A [2- phenoxyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : hydrogen atom, n=1], or SR-504 (ethoxylated nonylphenol acrylate, R ¹ : hydrogen atom, R ² : ethylene group, R ³ : n-nonyl group] and the like.

In the monomer represented by the general formula (19), the alkyl group of R ³ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Alkyl groups include not only linear alkyl groups, but also branched alkyl groups and alkyl groups having a benzene ring as a substituent. When the number of carbon atoms in the alkyl group of R ³ is 1 to 10, the alkyl group becomes an obstacle, suppressing the approach of the resins to each other and promoting adsorption/orientation to the pigment. The steric hindrance effect increases, and it tends to hinder even the adsorption/orientation of the benzene ring to the pigment. This tendency becomes more pronounced as the carbon chain length of the alkyl group of R ³ increases, and when the number of carbon atoms exceeds 20, the adsorption/orientation of the benzene ring is extremely reduced. Examples of the alkyl group having a benzene ring represented by R ³ include a benzyl group and a 2-phenyl(iso)propyl group. By increasing the side chain benzene ring by one, solvent affinity and pigment orientation are further improved, and not only dispersibility but also developability are improved.

In the monomer represented by formula (19), n is preferably an integer of 1-15. If n exceeds 15, the hydrophilicity increases and the solvation effect decreases, the viscosity of the vinyl resin increases, and the viscosity of the coloring composition using this increases, which may affect fluidity. There is From the viewpoint of solvation, n is more preferably 1-4.

The precursor of the structural unit (b2) having an aromatic ring group is styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or A monomer represented by the general formula (19) is preferred. By introducing a benzene ring into the side chain of the resin (B1), the side chain benzene ring is oriented to the pigment, which promotes resin adsorption to the pigment and also functions to suppress aggregation of the pigment. Further, benzyl acrylate and/or benzyl methacrylate are preferred from the viewpoint of developability, dispersion stability, and solvent shock.

The content of the structural unit (b2) having an aromatic ring group is preferably 2 to 80 mol%, based on the total monomer units of the alkali-soluble binder resin (B1), from the viewpoint of solvent shock resistance and developability. 60 mol % is more preferred, and 2 to 40 mol % is even more preferred. When contained in an appropriate amount, development resistance and substrate adhesion are further improved.

[Structural Unit (b3) Having Aliphatic Ring Group]
The structural unit (b3) having an alicyclic group has a cyclic structure with an alicyclic group represented by the following formulas (b31) and (b32). They are not compatible as affinity sites for dispersants of pigments and dyes and to alkaline developers. The content of the structural unit (b3) having an alicyclic group is preferably 2 to 80 mol% of the total monomer units of the binder resin (B1). This improves developability and further suppresses solvent shock.

The dicyclopentane moiety in the structure of the structural unit (b3) having an aliphatic ring group does not have a planar ring structure, and sterically hinders the aggregation of molecules in the filter segment. You can expect to give

Precursors of the structural unit (b3) having an aliphatic ring group include monomers represented by general formula (b33), monomers represented by general formula (b34), and the like.

[In general formulas (b33) and (b34), R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 or 3 carbon atoms, and m is 0 to 2 is an integer. ]

The monomer represented by the general formula (b33) is, for example, Funcryl FA-513 manufactured by Hitachi Chemical Co., Ltd.
A [dicyclopentanyl acrylate, R ¹ : hydrogen atom, R ² : none, m=0] or FA-513M [dicyclopentanyl methacrylate, R ¹ : hydrogen atom, R ² : none, m=0] etc. However, without being limited to these, two or more kinds can be used together.

The monomer represented by the general formula (b34) is, for example, Funcryl FA-511 manufactured by Hitachi Chemical Co., Ltd.
A [dicyclopentenyl acrylate, R ¹ : hydrogen atom, R ² : none, m=0], FA-512A [dicyclopentenyloxyethyl acrylate, R ¹ : hydrogen atom, R ² : ethylene group, m=1] , FA-512M [dicyclopentenyloxyethyl methacrylate, R ¹
: methyl group, R ² : ethylene group, m=1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ¹ : methyl group, R ² : ethylene group, m=1].

The content of the structural unit (b3) having an aliphatic ring group is preferably 2 to 80 mol%, more preferably 2 to 60 mol%, more preferably 2 to 80 mol% of the total monomer units of the alkali-soluble binder resin (B1). 40 mol % is more preferred. When contained in an appropriate amount, developability, development resistance, and substrate adhesion are improved, and solvent shock can be further suppressed.

[Carboxyl Group-Containing Structural Unit (b4)]
The carboxyl group-containing structural unit (b4) has a carboxyl group and functions as an alkali-soluble site during development. The carboxyl group-containing structural unit (b4) preferably accounts for 2 to 60 mol% of all monomer units in the alkali-soluble binder resin (B1). Developability, development resistance, and substrate adhesion can be improved when contained in an appropriate amount.

The precursor of the carboxyl group-containing structural unit (b4) is an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid, or α-chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumaric acid. carboxyl group-containing monomers. Compounds obtained by half-esterification of unsaturated dicarboxylic acid anhydrides such as maleic anhydride with hydroxyl group-containing (meth)acrylic compounds such as hydroxyalkyl (meth)acrylates are also included. Among these, (meth)acrylic acid is preferred, and methacrylic acid is more preferred, from the viewpoint of polymerizability (ease of control of molecular weight and the like).

Even if the compound contains a carboxyl group in the raw material stage, if the carboxyl group is changed into an ester bond or the like in the process of forming the binder resin (B), it does not correspond to the structural unit (b4).

[Other structural units (b5)]
The alkali-soluble binder resin (B1) can contain a structural unit (b5) other than the structural units (b1) to (b4). However, the structural unit (Bb-1) having a blocked isocyanato group is excluded.
Other monomers forming the structural unit (b5) include, 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, stearyl (meth)acrylate, lauryl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate ) acrylates, phenoxydiethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates, ethoxypolyethylene glycol (meth)acrylates and other (meth)acrylates;
2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) ) hydroxyl group-containing (meth)acrylates such as acrylates;
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 12- Polyester mono (meth) acrylates to which hydroxystearic acid or the like is added;
(Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamides such as acryloylmorpholine ;
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;
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-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl -2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6- N-substituted maleimides such as maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(Meth)acryloyloxyethyl acid phosphate, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing (meth)acrylate with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid, etc. containing a phosphoric acid ester group (Meth)acrylates and the like.

Raw materials for synthesizing the alkali-soluble binder resin (B1) can be used alone or in combination of two or more.

The content of the alkali-soluble binder resin (B1) is preferably 5% by mass or more and 95% by mass or less in 100% by mass of the alkali-soluble binder resin (B) from the viewpoint of developability and substrate adhesion, and 10% by mass or more and 90% by mass. % by mass or less is more preferable.

Alkali-soluble binder resin (B1) can be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the alkali-soluble binder resin (B1) is 5,000 to 50,000 from the viewpoint of heat resistance, development resistance, and compatibility with the alkali-soluble binder resin (Bb) containing a blocked isocyanato group. is preferred, and 6,000 to 30,000 is more preferred.

The acid value of the alkali-soluble binder resin (B1) is preferably 20-200 mgKOH/g, more preferably 40-150 mgKOH/g, from the viewpoint of developability.

(Alkali-soluble binder resin (B2))
The photosensitive coloring composition of the present invention contains, as the binder resin (B), an alkali-soluble binder resin (Bb) and an alkali-soluble binder resin (B2) other than the binder resin (B1) within a range that does not impair the effects of the present invention. can do.

The content of the binder resin (B) is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, and even more preferably 3 to 60% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition.

[Polymerizable compound (C)]
The photosensitive coloring composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that forms a film by photocuring.
The polymerizable compound (C) includes monomers and oligomers. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups. Examples of the polymerizable compound (C) include a lactone-modified polymerizable compound, a polymerizable compound having an acid group, a polymerizable compound having a urethane bond, and other polymerizable compounds.

(Lactone-modified polymerizable compound)
From the viewpoint of heat resistance, the photosensitive coloring composition of the present invention preferably contains a lactone-modified polymerizable compound.
A lactone-modified polymerizable compound is a compound having a lactone-modified structure in its molecule. The lactone-modified polymerizable compound includes polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethritol, tripentaerythritol, glycerin, diglycerol, and trimetholmelamine, and ( It is obtained by esterifying meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound is preferably a compound represented by the following general formula (24).

general formula (24)

In the general formula (24), all six R are groups represented by the following general formula (25), or 1 to 5 of the six R are groups represented by the following general formula (25) , and the rest are groups represented by the following general formula (26).

general formula (25)

In general formula (25), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond that bonds to the oxygen atom in general formula (24).

general formula (26)

In general formula (26), R ¹ represents a hydrogen atom or a methyl group, and * is a bond that bonds to the oxygen atom in general formula (24).

Lactone-modified polymerizable compounds are commercially available, for example, as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. DPCA-20 (in the above general formulas (24) to (26), m = 1, general formula (25 ) = 2, R ¹ are all hydrogen atoms), DPCA-30 (in the above general formulas (24) to (26), m = 1, in general formula (25) The number of groups represented = 3, a compound in which all R ¹ are hydrogen atoms), DPCA-60 (in the above general formulas (24) to (26), m = 1, the group represented by general formula (25) = 6, R ¹ are all hydrogen atoms), DPCA-120 (in the above general formulas (24) to (26), m = 2, the number of groups represented by general formula (25) = 6 , compounds in which all R ¹ are hydrogen atoms), and the like.

From the viewpoint of coating film resistance, the lactone-modified polymerizable compound has m = 1 in the general formulas (24) to (26), the number of groups represented by the general formula (25) = 2 to 6, R ¹ are all hydrogen atoms, and in the above general formulas (24) to (26), m = 1, the number of groups represented by general formula (25) = 2 or 3, and R ¹ are all hydrogen atoms. is more preferred.

From the viewpoint of heat resistance, the content of the lactone-modified polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and 20 to 60% by mass in 100% by mass of the polymerizable compound (C). % is more preferable.

(Polymerizable compound having acid group)
From the viewpoint of developability and pattern formation, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound having an acid group. Examples of the acid group of the polymerizable compound having an acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among these, a carboxyl group is preferred.

Polymerizable compounds having an acid group include, for example, esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid, and dicarboxylic acids; Examples thereof include esterified products with meth)acrylates.
Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, and itaconic phthalate.
Examples of polyvalent carboxylic acids include trimellitic acid and pyromellitic acid.
Monohydroxyalkyl (meth)acrylates, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and the like.

Commercial products of polymerizable compounds having an acid group include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd. is mentioned.

The content of the polymerizable compound having an acid group is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on 100% by mass of the polymerizable compound (C), from the viewpoint of developability and pattern formation. 15 to 80% by mass is more preferable.

(Polymerizable compound having urethane bond)
From the viewpoint of pattern formation, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound having a urethane bond as the polymerizable compound (C).

The polymerizable compound having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyhydric alcohol reacted with a polyfunctional isocyanate and further having a hydroxyl group. Urethane (meth)acrylate obtained by reacting (meth)acrylate, and the like.

The (meth)acrylate having a hydroxyl group is, for example, 2-hydroxyethyl (meth)
Acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene Oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy A reaction product of a group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like can be mentioned.

Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate. , their burettes, isocyanate nurates, trimethylolpropane adducts, and the like.

From the viewpoint of developability, the polymerizable compound having a urethane bond preferably further has an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among them, a carboxyl group is preferred.

In the method of introducing an acid group into a polymerizable compound having a urethane bond, for example, first, the (meth)acrylate having a hydroxyl group and the polyfunctional isocyanate are reacted. Then, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

Mercapto compounds having a carboxyl group include, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

The number of polymerizable unsaturated groups in the polymerizable compound having a urethane bond is preferably 3 to 15, more preferably 5 to 12, from the viewpoint of pattern formation.

From the viewpoint of pattern formation, the content of the polymerizable compound having a urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, more preferably 20 to 60% in 100% by mass of the polymerizable compound (C). % by mass is more preferred.

(Other polymerizable compounds)
Other 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) ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylo - Various acrylic and methacrylic esters such as (meth)acrylic esters of melamine, epoxy (meth)acrylates, urethane acrylates, 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.

Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R- 684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, and Aronix M-303, M-305, M-306, M-309, M manufactured by Toagosei Co., Ltd. -310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406 , M-450, M-452, M-408, M-211B, M-101A, M-3041, M-3042, M-7100, M-7300K, M-8530, M-8560, M-9050, Osaka Organic Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405, #1000LT, Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300, ABE-300 , A-DOG, A-DCP, A-BPE-4, EBECRY40, 130, 140, 145 manufactured by Daicel Allnex, AH-600 manufactured by Kyoeisha Chemical Co., AT-600, OGSOL EA manufactured by Osaka Gas Chemical Co., Ltd. -0200, 0300, 6361-100, 6362-100, 6363, DR-E522, 5104D, 63922, SP1106 from MIWON CN-2301, CN-2302, CN-2303, CN from Sartomer -2304, and the like.

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

The polymerizable compound (C) is selected from the group consisting of a lactone-modified polymerizable compound, an acid group-containing polymerizable compound, and a urethane bond-containing polymerizable compound, from the viewpoints of developability, pattern formation, and heat resistance. It is preferable to include one or more of the

The content of the polymerizable compound (C) is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition.

[Photoinitiator (D)]
The photosensitive coloring composition of the present invention contains an O-acyloxime ester photopolymerization initiator (D1). When the O-acyl oxime ester photopolymerization initiator (D1) absorbs ultraviolet rays, the N—O bond of the oxime is cleaved to generate 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.

(O-acyl oxime ester photopolymerization initiator (D1))
The O-acyl oxime ester photopolymerization initiator (D1) contains at least one of the compounds represented by the following general formulas (1) to (5).

(Oxime-based photopolymerization initiator (D1-1) represented by general formula (1))
General formula (1):

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. show. R ³ represents —COR ⁵ , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. ^R5 represents a phenyl group which may have a substituent. R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group, cyclic alkyl group, acyl group, and phenyl group of R ¹ to R ⁴ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. may The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with another substituent R ⁶ . ^R6 represents a halogen atom, fluorine atom, alkyl group, cyclic alkyl group, acyl group, nitro group, sulfo group and phenyl group.

Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R ¹ to R ⁴ in the general formula (1) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

Cyclic alkyl groups having 3 to 20 carbon atoms represented by R ¹ to R ⁴ in general formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.

The oxime photopolymerization initiator (D1-1) represented by the general formula (1) is, for example, 1-[9-ethyl-6-benzoyl-9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-benzoate,
Ethanone, 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), Ethanone, 1-(9-ethyl-6-benzoyl- 9H-carbazol-3-yl)-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl] -, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O- acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1- [9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6- {2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl -6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl -4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxy benzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazole -3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl} -9H-carbazol-3-yl]-,1-(O-acetyloxime) and compounds represented by the following chemical formulas (1-1) to (1-9).

Chemical formula (1-1)

chemical formula (1-2)

Chemical formula (1-3)

Chemical formula (1-4)

Chemical formula (1-5)

Chemical formula (1-6)

Chemical formula (1-7)

chemical formula (1-8)

Chemical formula (1-9)

(Oxime-based photopolymerization initiator (D1-2) represented by general formula (2))
General formula (2):

In general formula (2), R ¹ and R ² may each independently have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic substituent having 3 to 20 carbon atoms. Indicates a good alkyl group or phenyl group. R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group or a sulfo group. The alkyl group, cyclic alkyl group, acyl group and phenyl group of R ¹ to R ³ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. may R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the aryl group or arylalkyl group represented by R ⁴ may be further substituted with R ₂₁ , —OR ₂₁ , —COR ₂₁ , hydroxyl group, nitro group, cyano group, halogen atom, or —COOR ₂₁ , R ₂₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 _carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group, A hydrogen atom of the arylalkyl group may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with other substituents.

Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R ¹ to R ⁴ in the general formula (2) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

Cyclic alkyl groups having 3 to 20 carbon atoms represented by R ¹ to R ⁴ in general formula (2) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.

The aryl group having 6 to 30 carbon atoms represented by R ⁴ and R ²¹ in the above general formula (2) is, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, or any of the above alkyl groups. Examples include phenyl, biphenylyl, naphthyl, anthryl, etc., which are substituted one or more times.

Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ⁴ in the general formula (2) include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.

Examples of the oxime photopolymerization initiator (D1-2) represented by the general formula (2) include compounds represented by the following chemical formulas (2-1) to (2-4).

chemical formula (2-1)

chemical formula (2-2)

chemical formula (2-3)

chemical formula (2-4)

(Oxime-based photopolymerization initiator (D1-3) represented by general formula (3))
General formula (3):

In general formula (3), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. show. R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. The alkyl group, acyl group and phenyl group of R ¹ to R ³ may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. ^R4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or ^-COR6 . R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. The hydrogen atoms of the substituents in R ¹ to R ⁶ may be further substituted with other substituents.

Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R ¹ to R ⁵ in the general formula (3) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

Cyclic alkyl groups having 3 to 20 carbon atoms represented by R ¹ to R ⁵ in general formula (3) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl groups.

The heterocyclic groups having 4 to 20 carbon atoms represented by R ⁴ and R ⁷ in the general formula (3) are, for example, benzofuran, isobenzofuran, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzo 5- to 7-membered heterocycles such as oxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl and morpholinyl.

The aryl group having 6 to 30 carbon atoms represented by R ⁶ in the general formula (3) is, for example, phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, substituted with one or more of the above alkyl groups. phenyl, biphenylyl, naphthyl, anthryl and the like.

Examples of the arylalkyl group having 7 to 30 carbon atoms represented by R ⁶ in the general formula (3) include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.

Examples of the oxime photopolymerization initiator (D1-3) represented by the general formula (3) include compounds represented by the following chemical formulas (3-1) to (3-3).

chemical formula (3-1)

chemical formula (3-2)

chemical formula (3-3)

(Oxime-based photopolymerization initiator (D1-4) represented by general formula (4))
General formula (4):

In general formula (4), R ¹ and R ² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. show. R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. ^R4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group optionally interrupted by a hydroxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁵ may be further substituted with other substituents.

Linear or branched alkyl groups having 1 to 20 carbon atoms represented by R ¹ to R ⁵ in the general formula (4) are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

Cyclic alkyl groups having 3 to 20 carbon atoms represented by R ¹ , R ² , R ³ and R ⁵ in the general formula (4) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclodothesyl. and the like.

The oxime-based photopolymerization initiator (D1-4) represented by the general formula (4) is, for example, 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime ), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1,2-octanedione, 1-[4-(benzoyl)phenyl]-, 2 -(O-benzoyloxime), ethanone, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2-methylphenylthio)phenyl]- Octan-1-one-2-one oxime-O-acetate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[ 4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate , 1-[4-(2-methylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octane -1-one-2-one oxime-O-benzoate, 1-[4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate and the following chemical formula (4-1) ~ A compound represented by the chemical formula (4-6) can be mentioned.

Chemical formula (4-1):

Chemical formula (4-2):

Chemical formula (4-3):

Chemical formula (4-4):

Chemical formula (4-5):

Chemical formula (4-6):

(Oxime photopolymerization initiator (D1-5) represented by general formula (5))
general formula (5)

In general formula (5), R ₁ and R ₂ each independently represent R ₁₁ or -COR ₁₁ ,
R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, _an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms; The alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl,
R ₃ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and is represented by R ₃ The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl, and the aryl group, arylalkyl group or heterocyclic group represented by _R3 The hydrogen atoms of are further R ₂₁ , —OR ₂₁ , —COR ₂₁ , —SR ₂₁ , —NR ₂₂ R ₂₃ , —CONR ₂₂ R ₂₃ , —NR ₂₂ —OR ₂₃ , —NCOR ₂₂ —OCOR ₂₃ , —NR ₂₂ optionally substituted with COR ₂₁ , —OCOR ₂₁ , —SCOR ₂₁ , —OCSR ₂₁ , —COSR ₂₁ , —CSOR ₂₁ , a hydroxyl group, a nitro group, a cyano group, a halogen atom, or —COOR ₂₁ ;
R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom The hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ which represents a heterocyclic group of numbers 4 to 20 may further be a hydroxyl group, a nitro group, a cyano group, The alkylene portion of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ may be substituted with a halogen atom, hydroxyl group or carboxyl group, and may be -O-, - oxygen by S-, -COO-, -OCO-, -NR ₂₄ -, -NR ₂₄ CO-, -NR ₂₄ COO-, -OCONR ₂₄ -, -SCO-, -COS-, -OCS- or -CSO- Atoms may be interrupted 1 to 5 times under conditions where they are not adjacent,
R ₂₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; , the alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₄ may have a branched side chain or may be a cyclic alkyl,
_R4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom; n represents 0 or 1;

The alkyl groups having 1 to 20 carbon atoms represented by R ₃ , R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ in the general formula (5) are, for example, methyl, ethyl, propyl, isopropyl , butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl , hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

The aryl group having 6 to 30 carbon atoms represented by R ₃ , R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ in the general formula (5) is, for example, phenyl, tolyl, xylyl, ethyl Examples include phenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

The arylalkyl groups having 7 to 30 carbon atoms represented by R ₃ , R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ in the general formula (5) are, for example, benzyl, α-methylbenzyl , α,α-dimethylbenzyl, phenylethyl and the like.

The heterocyclic groups having 2 to 20 carbon atoms represented by R ₃ , R ₁₁ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ in the general formula (5) are, for example, pyridyl, pyrimidyl, furyl, 5- to 7-membered heterocycles such as thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, and morpholinyl; be done.

The method for producing the oxime-based photopolymerization initiator (D1) represented by the general formula (5) is not particularly limited, and known methods can be used. For example, the method described in WO2015/152153 can be used.

Examples of the oxime photopolymerization initiator (D1-5) represented by the general formula (5) include compounds represented by the following chemical formulas (5-1) to (5-8).

Among these O-acyloxime compounds, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)- 9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) Methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyloxime) is preferred.

Commercial products include 1,2-octanedione,1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (IRGACURE OXE-01) manufactured by BASF, IRGA
CURE OXE-03, IRGACURE OXE-04, N-1919 manufactured by ADEKA, NCI-730, NCI-831, NCI-930, TRONLYTR-PBG-304 and TRONLY TR-PBG-305 manufactured by Changzhou Tenryu New Materials Co., Ltd. TRONLY TR-PBG-3057, TRONLY TR-PBG-309, TRONLY TR-PBG-345, TRONLY TR-PBG-3054 and the like. In addition, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, International Publication WO2015/036910, etc. Also included are the oxime compounds described.

Among these, from the viewpoint of pattern formability and substrate adhesion, TRONLY TR-PBG
-345, NCI-730 and NCI-930 are more preferred, and IRGACURE OXE-04 and NCI-831 are even more preferred.

<Other photopolymerization initiators>
Photopolymerization initiators other than the above include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-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 - acetophenone compounds such as butanone; 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, Thioxanthone compounds such as 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; bis(2,4,6-trimethylbenzoyl)phenyl phosphine compounds such as sphinoxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole-based compounds; or titanocene-based compounds.

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

The content of the photopolymerization initiator (D) is 0.04 to 200 parts by mass with respect to 100 parts by mass of the dye (A) from the viewpoint of development speed, solvent resistance, substrate adhesion, development stains, and tapered shape. parts is preferred, and 0.1 to 100 parts by mass is more preferred. When blended in an appropriate amount, solvent resistance, substrate adhesion and development stains are further improved.

[Leveling agent (E)]
The photosensitive coloring composition of the present invention contains a leveling agent (E). This further improves the wettability and dryability of the substrate during coating. Examples of the leveling agent (E) include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants. Further, the photosensitive coloring composition containing the alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group of the present application has a high affinity between the blocked isocyanato group and the developer, so that the coating film surface after development Stain easily occurs (development stain). However, it was found that the combination of the O-acyl oxime ester photopolymerization initiator (D1) and the above leveling agent significantly improved the performance.

(Silicone-based surfactant (E1))
Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Commercially available products are, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377 manufactured by BYK Chemie, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110, 2122, 2123, 2191, 5609, SH-8400, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22- 4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc. is mentioned.

(Fluorine-based surfactant (E2))
Fluorosurfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

Commercially available products are, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd., and Megafac F-253, 477, 551, 552, 554, 555, 558, 560 manufactured by DIC Corporation. , 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M FC-4430, 4432, Mitsubishi Materials Electronic Chemicals EF-PP31N09, EF -PP33G1, EF-PP32C1, Neos Ftergent 601ADH2, 602A, Fluorosurf FS-7024, FS-7025, FS-7026, FS-7027, FS-7031, FS-7032, Shin-Etsu Chemical Co., Ltd. KY-1203, KY-1207, KY-1211, X-71-1203E, etc. of

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleic acid Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamides, alkylimidazolines, and the like.

Commercially available products are, for example, Kao Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Rhodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31 manufactured by ADEKA, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow-No. 75, No. 90, No. 95 and the like.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Commercially available products include, for example, Acetamine 24, Kotamine 24P, 60W, 86P conch manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenylether disulfonates, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos, Adeka Hope YES-25, Adekacol TS-230E, PS-440E and EC-8600 manufactured by ADEKA.

Amphoteric surfactants include, for example, lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Commercially available products include Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

A leveling agent (E) can be used individually or in combination of 2 or more types.

The content of the leveling agent (E) is preferably 0.001 to 3.0% by mass, more preferably 0.005 to 1.2% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the balance between coatability, adhesion, development stain resistance, and solvent resistance of the photosensitive coloring composition is further improved. From the viewpoint of development stains, the silicone-based surfactant (E1) and the fluorine-based surfactant (E2) are particularly preferred.

Among these, BYK-330, BYK-323 and 348 manufactured by BYK-Chemie, FZ-2122 and SH-8400 manufactured by Dow Corning Toray, Ftergent 601ADH2 manufactured by NEOS, and 602A, Fluorosurf FS-7024, FS-7025, FS-7026, FS-7027, FS-7031, FS-7032 manufactured by Fluorotechnology, KY-1203, KY-1211 manufactured by Shin-Etsu Chemical Co., Ltd., Mega manufactured by DIC Fac F-554 is more preferred.

[Thermal base generator (F)]
The photosensitive coloring composition of the present invention may contain a thermal base generator together with an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group. By containing the thermal base generator (F) together with the alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group, the release of the blocking agent from the blocked isocyanato group is accelerated and the curing speed is accelerated. effect is obtained. As the thermal base generator (F), known or commonly used curing accelerators can be used without particular limitation, but examples include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and salts thereof (e.g., phenol salts, octylate salts, p-toluenesulfonate salts, formate salts, tetraphenylborate salts); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and its Salts (eg phenol salts, octylate, p-toluenesulfonate, formate, tetraphenylborate salts); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethyl Tertiary amines such as cyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters, triphenylphosphine (TPP), and salts thereof ( phosphines such as tetrafluoroborate salts and triphenylborane salts; phosphonium compounds such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium tetra(p-tolyl)borate; organic metals such as tin octylate and zinc octylate salts; metal chelates; These can be used individually by 1 type or in combination of 2 or more types.

Commercially available products include, for example, U-CAT SA 1, U-CAT SA 506, U-
CAT SA 102, U-CAT 5003, U-CAT 1102, U-CAT 18X
, U-CAT 12XD, U-CAT 3512T, TPP-K and TPP-MK manufactured by Hokko Chemical Industry Co., Ltd., PX-4ET manufactured by Nippon Chemical Industry Co., Ltd., and the like.

[Sensitizer (G)]
From the viewpoint of pattern formability, the photosensitive coloring composition of the present invention preferably contains a sensitizer (G).

Sensitizers (G) include, for example, chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzyl and camphorquinone, benzoin compounds, and fluorene. Polymethines such as polymethine-based compounds, naphthoquinone-based compounds, anthraquinone-based compounds, xanthene-based compounds, thioxanthene-based compounds, xanthone-based compounds, thioxanthone-based compounds, coumarin-based compounds, ketocoumarin-based compounds, cyanine-based compounds, merocyanine-based compounds, and oxonol-based compounds dyes, acridine-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indoline-based compounds, azulene-based compounds, azulenium-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, Tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds compounds, tetraphylline-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, benzophenone-based compounds, and the like. Among these, from the viewpoint of pattern formation, the thioxanthone compound (G1) or the benzophenone compound (G2) is preferred, and the thioxanthone compound (G1) is more preferred.

(Thioxanthone-based compound (G1))
Thioxanthone compounds (G1) include, for example, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. be done. Among these, 2,4-diethylthioxanthone is preferred.

Commercially available products include Omnirad DETX manufactured by IGM RESINS and KAYACURE DETX-S manufactured by Nippon Kayaku.

(Benzophenone compound (G2))
Benzophenone compounds (G2) include, for example, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 2-aminobenzophenone and the like. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

Commercially available products include CHEMARK DEABP manufactured by CHEMARK CHEMICAL.

A sensitizer (G) can be used individually or in combination of 2 or more types.

From the viewpoint of pattern formation, the content of the sensitizer (G) is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D).

[Thermosetting compound (H)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (H). As a result, the thermosetting compound (H) reacts in the heating step, increasing the crosslink density and improving the heat resistance.

The thermosetting compound (H) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Thermosetting compounds (H) include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (H1))
Epoxy compounds (H1) 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 dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) polycondensates of phenols and ketones (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.), phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, and the like.

Commercially available products include, for example, EPICOAT 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H manufactured by Nippon Kayaku, EOCN-102S, 103S, 104S, 1020 Epikote 1004, 1256 manufactured by Japan Epoxy Resin, JER1032H60, 157S65, 157S70, 152, 154, Celloxide 2021 manufactured by Daicel Chemical Industries, EHPE-3150, TTA3150 manufactured by Tetrachem, Nagase Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Chemtex, TEPIC- manufactured by Nissan Chemical Industries, Ltd. L, H, S etc. are mentioned.

From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (H1) is preferably 0.5 to 30 parts by mass, and 1.0 to 20 parts by mass, based on 100 parts by mass of the nonvolatile matter of the photosensitive coloring composition. part is more preferred.

(Oxetane compound (H2))
The oxetane compound (H2) is a known compound having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-
Hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl -3-{[3-(triethoxysilyl)propoxy]methyl}oxetane and the like.

Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Bifunctional oxetane compounds include, for example, 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3 -ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)- 5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol-bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3 -ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3- ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) methyl) ether and the like.

Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

Trifunctional or higher oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups ( For example, oxetane-modified phenolic novolak resins described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30 can be mentioned.

The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition.

A melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol-type or ether-type compound, and more preferably a melamine compound having an average number of methylol groups and/or ether groups of 5.0 or more per melamine ring. Having an appropriate number of methylol groups and ether groups makes it easy to obtain just the right amount of heat resistance.

Commercially available products include, for example, Sanwa Chemical Co., Ltd. Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX- 417, MX-410, and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries.

Among these, Nicarac MW-30HM, MW-390, MW-100LM and MX manufactured by Sanwa Chemical Co., Ltd., having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. -750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cymel 232, 235, 236, 238, 300 manufactured by Nippon Cytec Industries Co., Ltd. , 301, 303, 350 and the like are preferable in terms of increasing the crosslink density.

A thermosetting compound (H) can be used individually or in combination of 2 or more types.

[Curing agent (curing accelerator)]
The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to assist curing of the thermosetting compound (H). Curing agents include, for example, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Curing agents include, for example, amine compounds (eg, 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 their salts (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.).

Curing agents can be used alone or in combination of two or more.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

[Thiol-based chain transfer agent (I)]
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (I). The thiol-based chain transfer agent (I), when used in combination with the photopolymerization initiator (D), generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen during radical polymerization after light irradiation, and increases the photosensitivity of the photosensitive coloring composition. improves.

The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

Polyfunctional thiols are, for example, hexanedithiol, decanedithiol, 1,4-butanedi-rubisthiopropionate, 1,4-butanedi-rubisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto tris(2-hydroxyethyl) isocyanurate propionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[Adhesion improver (J)]
The photosensitive coloring composition of the present invention can contain an adhesion improver (J). This improves the adhesion between the cured film and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.

Adhesion improvers (J) include, for example, silane coupling agents. Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, 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-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include silane coupling agents such as sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

Adhesion improvers (J) can be used alone or in combination of two or more.

The content of the adhesion improver (J) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the nonvolatile matter of the photosensitive coloring composition.

[Polymerization inhibitor (K)]
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (K).
The polymerization inhibitor (K) is, for example, 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-t-butylcatechol, 3-t-butylcatechol , 4-t-butylcatechol, 3,5-di-t-butylcatechol and other alkylcatechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 alkylresorcinol compounds such as -propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzyl phosphine compounds such as phosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite;

The content of the polymerization inhibitor (K) is preferably 0.01 to 0.4 parts by mass in 100 parts by mass of the non-volatile matter of the photosensitive coloring composition.

[Ultraviolet absorber (L)]
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (L).
The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylate-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. compounds and the like.

Benzotriazole compounds include, for example, 2-(5methyl-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- dimethylethyl)-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.

Commercially available products are, for example, TINUVIN P, PS, 234, 32 manufactured by BASF Japan.
6,329,384-2,900,928,99-2,1130, Adekastab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA, KEMISORB71, 73, 74 manufactured by Chemipro Kasei, 79,279, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

Triazine compounds include, for example, 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-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis'2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, AD
Adekastab LA-46 and LA-F70 manufactured by EKA, CYASORB UV-1164 manufactured by Sun Chemical Co., etc. may be mentioned.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 5-sulfonic acid-3, water temperature, 2-hydroxy-4-n-octo xybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octa decyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. .

Commercially available products are, for example, KEMISORB 10, 11, 11S, 12 manufactured by Chemipro Kasei Co., Ltd.
, 111, SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

The content of the ultraviolet absorber (L) is preferably 5 to 90% by weight based on the total 100% by weight of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[Antioxidant (M)]
The photosensitive coloring composition of the present invention can contain an antioxidant (M). The antioxidant (M) prevents the photopolymerization initiator (D) and the thermosetting compound (I) from yellowing due to oxidation during thermal curing and ITO annealing. In particular, when the concentration of the photosensitive coloring pigment (A) is high, the content of the polymerizable compound (C) is relatively reduced. Then, the cured film tends to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. Antioxidant (M) is preferably a compound containing no halogen atom.

Antioxidants (M) include, for example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6 ( 1H,3H,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2 -t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4, 8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1, 3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2 '-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylene Bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6- Bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis [3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanedi-rubis[3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2′-thio -bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis - (4, 6-dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. is mentioned.

Commercially available products include, for example, ADEKA's Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, and Chemipro's KEMINOX 101, 179, 76, 9425. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., etc. mentioned.

Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensates of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) Amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)decanedioate -4-piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1, 1 dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1, 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide etc.

Commercially available products are, for example, ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 , LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, Cyasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3529, UV-3853 and the like.

Phosphorus antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2′-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15alkyl)-4,4' -Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-t-butyl-6-methylphenyl) and the like.

Commercial products include, for example, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. -EPQ and the like.

Sulfur antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3′- ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like.

Commercially available products include, for example, ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei.

Antioxidants (M) can be used alone or in combination of two or more.

The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

[Storage stabilizer (N)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. Storage stabilizers (N) 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, tetraphenyl and the like. organic phosphines, phosphites, and the like.

The content of the storage stabilizer (N) is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the nonvolatile matter of the photosensitive coloring composition.

[Organic solvent (Q)]
The photosensitive coloring composition of the present invention can contain an organic solvent (Q).
Organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 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-cyclohexene-1-
On, 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, N-methylpyrrolidone, 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 monoisopropyl 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, 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 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 , 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 these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like are preferred from the viewpoint of pigment dispersibility and alkali-soluble resin solubility. Alcohols such as glycol acetates, benzyl alcohol, diacetone alcohol, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and ketones such as cyclohexanone are preferred.

The organic solvent (Q) can be used alone or in combination of two or more.

[Method for producing a photosensitive coloring composition]
The photosensitive coloring composition of the present invention, for example, by adding a dye (A), a resin-type dispersant (Z), an organic solvent (Q), etc., and performing a dispersion treatment, produces a dispersion. After that, the binder resin (B), the polymerizable compound (C), the photopolymerization initiator (D) and the like are added to the dispersion and mixed to produce the dispersion. The timing of blending each material is arbitrary. Moreover, a dispersion|distribution process can also be performed in multiple times.

Examples of the dispersing machine for performing the dispersing treatment include a two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, and attritor.

The average dispersed particle size (secondary particle size) of the dye (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particle size is appropriate, a photosensitive coloring composition with high dispersion stability can be easily obtained.

The method for measuring the average dispersed particle size (secondary particle size) is, for example, using a Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs the dynamic light scattering method (FFT power spectrum method), and the particle permeability is measured by the absorption mode. The particle shape is assumed to be non-spherical, and the D50 particle diameter is defined as the average diameter. It is preferable to use the organic solvent used for dispersion as the diluent solvent for the measurement, and to measure the ultrasonically treated sample immediately after the sample preparation, because it is easy to obtain results with little variation.

The photosensitive coloring composition is separated from coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, filtration with a sintered filter or membrane filter, and It is preferable to remove mixed dust. The photosensitive coloring composition of the present invention preferably contains substantially no particles of 0.5 μm or more, more preferably no particles of 0.3 μm or less.

<Cured film>
The cured film of the present invention is obtained by curing a film formed using the photosensitive coloring composition of the present invention by exposure or other treatment.

[Method for producing cured film]
The method for producing the cured film is not particularly limited, for example, the step (1) of applying a photosensitive coloring composition on a substrate to form a layer of the composition, and exposing the layer in a pattern through a mask. It can be produced by performing the step (2), the step (3) of alkali-developing the unexposed portion to form a patterned cured film, and the step (4) of heat-treating (post-baking) the pattern.

The method for producing a cured film will be described in detail below.
(Step (1))
In step (1) of forming a layer of the composition, the photosensitive coloring composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, If necessary, it is dried (pre-baked) at a temperature of 50 to 120° C. for 10 to 120 seconds using an oven, hot plate, or the like.
Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have, for example, an imaging element such as a CCD or CMOS formed on its surface. In addition, if necessary, an undercoat layer may be provided on the substrate for improving adhesion with the upper layer, preventing diffusion of substances, and flattening the surface of the substrate.
The thickness of the layer after drying is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

(Step (2))
In the exposure step, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. A cured film is thus obtained.
Radiation used for exposure includes, for example, ultraviolet rays such as g-line, h-line and i-line.

(Step (3))
The cured film obtained in step (2) is subjected to alkali development treatment, whereby the layer of the composition in the unexposed portions is eluted in an alkaline aqueous solution, leaving only the cured portions to obtain a patterned cured film.
Developers include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11-13, more preferably 11.5-12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed, and the residual film rate after development can be improved.

The developing method includes, for example, a dipping method, a spraying method, a paddling method and the like. The developing temperature is preferably 15 to 40°C. In addition, it is preferable to wash with pure water after alkali development.

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 100 to 300.degree. C., more preferably 150 to 250.degree. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

<Color filter>
The cured film of the present invention can be used for color filters. A color filter can cut part of the transmitted light.

<Optical filter>
The cured film of the present invention can be used for optical filters. Among the optical filters, an infrared cut filter and an infrared transmission filter are preferable. In this specification, the optical filter can be manufactured by the same method as the cured film described above.

<Image display device>
The cured film of the present invention can be used in image display devices. The form used for the image display device is not particularly limited, but it can be used as a near-infrared cut filter, a near-infrared pass filter, a color filter, or a black matrix.
The black matrix is a solid-state imaging device, a black edge provided at the periphery of an image display device such as a liquid crystal display device, a grid-shaped and / or striped black portion between red, blue, and green pixels, Dot and/or linear black patterns for TFT light shielding may be used.

An example of the image display device of the present invention will be described.
An image display device comprises the cured film of the present invention and a light source. A cold cathode fluorescent lamp (CCFL), a white LED, and an organic EL element can be used as the light source. FIG. 1 is a schematic cross-sectional view showing a configuration example of an image display device provided with the cured film of the present invention. The image display device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged facing each other with a gap between them, and a liquid crystal LC is enclosed between them.

A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

Liquid crystal LC is TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated
Birefringence) is oriented according to the driving mode. first transparent substrate 1
A TFT (Thin Film Transistor) array 12 is formed on the inner surface of 1, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

On the other hand, a color filter 22 is formed on the inner surface of the second transparent substrate 21 . The red, green and blue filter segments that make up color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . A backlight unit 30 is provided below the polarizing plate 15 .

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, and the ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation), NSSW304D-HG-V1 (manufactured by Nichia Corporation), and the like.

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

<Solid-state image sensor>
The cured film of the present invention can be used for solid-state imaging devices. The form used for the solid-state imaging device is not particularly limited. A mode having a light-receiving element made of a diode and polysilicon or the like and having the cured film of the present invention on the light-receiving element formation surface side or the opposite side of the formation surface can be exemplified. FIG. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device provided with the cured film of the present invention.

As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging device 201 and a transparent cover glass 203 that is held above the solid-state imaging device 201 and seals the solid-state imaging device 201. there is Further, a lens layer 211 is provided over the cover glass 203 with spacers 104 interposed therebetween. The lens layer 211 is composed of a support 213 and a lens material 212 . When stray light enters the peripheral region of the lens layer 211 , light diffusion weakens the light condensing effect of the lens material 212 , reducing the amount of light that reaches the imaging unit 202 . Also, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 211 is provided with the cured film 214 of the present invention to shield light.

The solid-state imaging device 201 photoelectrically converts an optical image formed by an imaging unit 202 serving as a light-receiving surface thereof, and outputs it as an image signal. This solid-state imaging device 201 has a laminated substrate 205 in which two substrates are laminated. The laminated substrate 205 is composed of a rectangular chip substrate 206 and a circuit substrate 207 of the same size.

An imaging unit 202 is provided in the central portion of the surface of the chip substrate 206 . In addition, when stray light is incident on the peripheral region of the imaging unit 202, dark current (noise) is generated from circuits in this peripheral region. It is

A plurality of electrode pads 208 are provided on the surface edge of the chip substrate 206 . The electrode pads 208 are electrically connected to the imaging section 202 via signal lines (not shown) provided on the surface of the chip substrate 206 .

External connection terminals 209 are provided on the rear surface of the circuit board 207 at positions substantially below the respective electrode pads 208 . Each external connection terminal 209 is connected to an electrode pad 208 via a through electrode 210 vertically penetrating through the laminated substrate 205 . In addition, each external connection terminal 209 is connected to a control circuit for controlling driving of the solid-state imaging device 201 and an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging device 201 via wiring (not shown). It is connected.

<Infrared sensor>
The cured film of the present invention can be used for infrared sensors. FIG. 3 is a schematic cross-sectional view showing a configuration example of an infrared sensor provided with the cured film of the present invention. The infrared sensor 300 shown in FIG.

An imaging area provided on the solid-state imaging device 310 is configured by combining an infrared cut filter 311 and a color filter 312 .
The infrared absorption filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm).
The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region. For example, pixels of red (R), green (G), and blue (B) are formed. A color filter or the like is used.

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 is arranged that allows transmission of the light of the wavelength that has passed through the infrared transmission filter 313. As shown in FIG.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and the cured film of the present invention containing the above-described near-infrared absorption dye can be used. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

A microlens 315 is arranged on the incident light side of the color filter 312 and the infrared transmission filter 313 . A planarization film 316 is formed to cover the microlenses 315 .

Although the resin film 314 is arranged in the form shown in FIG.

The cured film of the present invention can be used as a light shielding film such as the edge and / or side of the surface of the infrared cut filter 311, and if it is used for the inner wall of the infrared sensor device, it can be used for internal reflection and / or meaningless light to the light receiving part. can be prevented from entering, and the sensitivity can be improved.

According to this infrared sensor, since image information can be captured at the same time, it is possible to perform motion sensing, etc., by recognizing an object whose motion is to be detected. In addition, since distance information can be obtained with this infrared sensor, it is possible to take an image including 3D information. Furthermore, this infrared sensor can also be used as a biometric sensor.

Moreover, the cured film of the present invention can also be used as a colored spacer. For example, when spacers are used in a TFT-type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and the colored spacer is used to prevent this. The colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.

The cured film of the present invention can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members imparting light shielding properties and antireflection properties.
Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

Moreover, the cured film of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as members imparting light shielding properties and antireflection properties.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these. In addition, "part" is "mass part" and "%" is "mass%". In addition, in the present invention, non-volatile matter or non-volatile matter concentration refers to the mass residue after standing in an oven at 280° C. for 30 minutes.

Prior to Examples, each measuring method will be described.
The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g), amine value (mgKOH/g), and glass transition temperature (Tg) of the resin are measured as follows.

(Average molecular weight of binder resin and resin-type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin and resin type dispersant were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40 ° C. , using a tetrahydrofuran (THF) solution as an eluent and measuring at a flow rate of 0.35 ml/min. Samples were dissolved in a solvent consisting of 1 wt % of the above eluent and injected at 20 microliters. A molecular weight is a polystyrene conversion value.

(Binder resin and acid value of resin type dispersant)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the binder resin and resin-type dispersant solution and stir to dissolve uniformly. COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) was used to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant is a value obtained by converting the total amine value (mgKOH/g) measured according to the method of ASTM D 2074 into the non-volatile content.

(Glass-transition temperature)
The glass transition temperature of the binder resin (B) was measured using a differential scanning calorimeter by weighing 5 mg of a sample into a sample pan and measuring the temperature from −20 to 200° C. at a heating rate of 10° C./min under a nitrogen stream.

<Production of dye (A)>
<Production of micronized pigment>

(Production of finely divided pigment A-R177)
anthraquinone red pigment C.I. I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Sinic Co.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. bottom. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. and finely divided organic pigment (A-R177)
got
(Production of micronized pigment A-R254)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 ("Irgajin RedL 3630" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. and finely divided organic pigments (A-R
254) was obtained.
(Production of micronized pigment A-R291)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 291: 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120° C. for 8 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided organic pigment (A-R291).

<Production of finely divided pigments (A-Y1) to (A-Y3)>
The following quinophthalone compounds (a) to (c) were prepared according to the examples of JP-A-2012-226110.

(Production of micronized pigment (A-Y1))
100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), kneaded at 60° C. for 6 hours, and subjected to salt milling. The resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , 98 parts of finely divided pigment (A-Y1) were obtained.

(Production of finely divided pigment (A-Y2))
100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 98 parts of finely divided pigment (A-Y2) were obtained.

(Production of micronized pigment (A-Y3))
100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of finely divided pigment (A-Y3) were obtained.

(Production of finely divided pigment A-Y138)
quinophthalone-based yellow pigment C.I. I. Pigment Red Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF Japan) 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. for 6 hours. Kneaded. This mixture is poured into 2,000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then dried at 80°C for a day and night to obtain a finely divided yellow pigment. (A-Y138) was obtained.

(Production of finely divided pigment A-Y139)
isoindoline yellow pigment C.I. I. 100 parts of Pigment Red Yellow 139 (Paliotol Yellow D1819 manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60° C. for 10 hours. and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and the solvent, and then dried at 80°C for one day and night. A finely divided organic pigment (A-Y139) was obtained.

(Refined pigment (A-Y150))
Metal complex yellow pigment (C.I. Pigment Red Yellow 150, Lanxess "Yellow Pigment E4GN") 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). , and kneaded at 60° C. for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided organic pigment (A-Y150).

(Production of yellow pigment (A-Y4))
(azobarbituric acid precursor)
An azobarbituric acid precursor was prepared according to the synthetic method described in JP-A-2017-171915. (Instruction 1)
46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were introduced into 1100 g of distilled water at 85°C. The pH was then adjusted to about pH 5 using aqueous potassium hydroxide and stirring continued for 90 minutes.
(Yellow pigment (Y4-1))
The azobarbituric acid precursor (0.3 mol) prepared in Instruction 1 was mixed with 1500 parts of distilled water at 82°C. 10 parts of 30% strength hydrochloric acid are then added dropwise to adjust the pH to 2-2.5. Thereafter, 79.4 parts melamine (0.
63 mol) were introduced. 0.3 mol of an approximately 25% strength nickel chloride solution was then added dropwise. After 3 hours at 82° C., the pH was adjusted to approximately 5.5 using KOH. This was followed by dilution with about 100 parts distilled water at 90°C. 21 parts of 30% strength hydrochloric acid are then added dropwise and a temperature of 90° C. is maintained for 12 hours. The pH was then adjusted to about 5 using aqueous potassium hydroxide. The pigment was then isolated on a suction filter, washed, dried in a vacuum drying cabinet at 80° C. and ground in a standard laboratory mill for 2 minutes. (Yellow pigment (Y4-1) = adduct of nickel azobarbituric acid and melamine).

(Yellow pigment (Y4-2))
"0.3 mol of about 25% strength nickel chloride solution" of the preparation example of yellow pigment (Y4-1) was replaced with "0.225 mol of 25% strength nickel chloride + 0.075 mol of 25% strength chloride A yellow pigment (Y4-2) was obtained in the same manner as the yellow pigment (Y4-1), except that the mixed solution of copper (II) was substituted. (Yellow pigment (Y4-2) = melamine adduct of copper/nickel azobarbituric acid, a hybrid compound with 25 mol% copper and 75 mol% nickel components)

(Yellow pigment (Y4-3))
"0.3 mol of about 25% strength nickel chloride solution" of the preparation example of yellow pigment (Y4-1) was replaced with "0.150 mol of 25% strength nickel chloride + 0.150 mol of 25% strength chloride A yellow pigment (Y4-3) was obtained in the same manner as the yellow pigment (Y4-1) except that it was replaced with a mixed solution of zinc. (Yellow Pigment (Y4-3) = melamine adduct of zinc/nickel azobarbituric acid, a hybrid compound with components of 25 mol% Zn and 75 mol% nickel)

(Yellow pigment (Y4-4))
"0.3 mol of about 25% strength nickel chloride solution" of the preparation example of yellow pigment (Y4-1) was replaced with "0.075 mol of 25% strength nickel chloride + 0.225 mol of 25% strength chloride A yellow pigment (Y4-4) was obtained in the same manner as the yellow pigment (Y4-1) except for replacing it with "mixed solution of zinc". (Yellow pigment (Y4-4) = melamine adduct of zinc/nickel azobarbituric acid, a hybrid compound with 50 mol% Zn and 50 mol% nickel components)

(Yellow refined pigment (A-Y4))
25 parts of yellow pigment (Y4-1), 25 parts of yellow pigment (Y4-2), 25 parts of yellow pigment (Y4-3), 25 parts of yellow pigment (Y4-4), 1000 parts of sodium chloride, and 120 parts of diethylene glycol A 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) was charged and kneaded at 70° C. for 8 hours. This mixture is poured into 2000 parts of warm water, heated to about 80°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80°C for 24 hours. After drying, a yellow finely divided pigment (A-Y4) was obtained.

(Micronized green pigment (A-G58))
C. I. 100 parts of Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A finely divided green pigment (A-G58) was obtained by drying and pulverizing.

(Micronized green pigment (A-G59))
C. I. Pigment Green 59 (100 parts), sodium chloride (1,200 parts), and diethylene glycol (120 parts) were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water, stirred for 1 hour with a high-speed mixer while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then kept at 80° C. for a day and night. A finely divided green pigment (A-G59) was obtained by drying and pulverizing.

(Micronized green pigment (A-G63))
C. I. 100 parts of Pigment Green 63, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine green pigment (A-G63).

(Micronized green pigment (A-G7))
C. I. 100 parts of Pigment Green 7 (Lionol Green 8390 manufactured by Toyocolor Co., Ltd.), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. bottom. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine green pigment (A-G7).

(Micronized green pigment (A-G36))
C. I. 100 parts of Pigment Green 36 (Lionol Green 6YK manufactured by Toyocolor Co., Ltd.), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 6 hours. bottom. Next, the kneaded mixture is put into hot water, heated to about 80°C and stirred with a high-speed mixer for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then heated to 80°C. It was dried for a whole day and night and pulverized to obtain a fine green pigment (A-G36).

(Micronized blue pigment (A-B156))
C. I. 100 parts of Pigment Blue 15:6 (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and heated at 50 ° C. Kneaded for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. It was dried for 24 hours and pulverized to obtain a finely divided blue pigment (A-B156).

(Micronized blue pigment (A-B153))
C. I. 100 parts of Pigment Blue 15:3 (“Lionol Blue FG7351” manufactured by Toyocolor Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and heated at 50 ° C. Kneaded for 12 hours. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. It was dried for 24 hours and pulverized to obtain a finely divided blue pigment (A-B153).

(Micronized purple pigment (A-V23))
C. I. 100 parts of Pigment Violet 23 (“Rionogen Violet FG6140” manufactured by Toyocolor Co., Ltd.), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and heated at 50° C. for 12 hours. Time kneaded. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After drying for 24 hours and pulverizing, a finely divided purple pigment (AV23) was obtained.

<Production of resin 1 having a cationic group in the side chain>
(Resin 1 solution having a cationic group in the side chain)
33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, and 27.3 parts of 2-ethylhexyl methacrylate were charged into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was raised to 100°C under a nitrogen stream to initiate polymerization of the first block. bottom. After polymerization for 4 hours, the polymerization solution was sampled and solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile matter. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of methacrylic acid dimethylaminoethylmethyl chloride salt as a second block monomer were added to the reactor, and stirred while maintaining the temperature at 100°C under a nitrogen atmosphere. , continued the reaction. Two hours after the introduction of the dimethylaminoethyl methyl chloride salt of methacrylate, the polymerization solution was sampled and the solid content was measured. cooled to Thereafter, methanol was added to obtain a resin (E-1) having a cationic group in a side chain and containing 40% by mass of the resin component. The weight average molecular weight (Mw) of Resin (E-1) was 7,300.

(Production of dye solutions A-D1 to D3)
(Dye 1)
To 2000 parts of water was added 30 parts of resin 1 solution having a cationic group on a side chain in terms of non-volatile content, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration is performed, and after washing with water, salt-forming compounds remaining on the filter paper are dried by removing moisture with a drier. I. A coloring agent (dye 1) was obtained as a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.

(Dye 2)
C. I. Add Acid Red 52 to C.I. I. The procedure was carried out in the same manner as in the preparation of the coloring agent (dye 1) except that C.I. Acid Red 289 was used. I. A coloring agent (dye 2) was obtained as a salt-forming compound of Acid Red 289 and resin 1 having a cationic group in the side chain. At this time, the C.I. I. The content of the active pigment component derived from Acid Red 289 was 27% by mass.

(Dye 3)
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 5.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1-(3-dimethylaminopropyl)-3-ethyl 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water, dried under reduced pressure, and purified with a silica gel column to obtain a coloring agent (dye 3).

<Production of dye solution A-D1>
The following mixture was uniformly stirred and mixed, and then filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (dye solution A-D1).
Coloring agent (dye 1) 20.0 parts Propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc)
50.0 parts Solvent (Q) 30.0 parts The solvent (Q) is a mixed solvent (Q) in which the following (Q-1) to (Q-4) are blended in parts by mass.
(Q-1) 33 parts of PGMAc (Q-2) 20 parts of 3-methoxybutanol (Q-3) 20 parts of ethyl 3-ethoxypropionate (Q-4) 20 parts of n-butyl acetate

(Production of dye solutions A-D2 and A-D3)
Dye solutions AD2 and AD3 were prepared in the same manner as dye solutions AD1, respectively, using colorants (dye 2 and dye 3).

<Production of near-infrared absorbing dye>
(Near-infrared absorbing dye (A-NIR1))
40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated with stirring and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the solution was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation.
After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture. After filtering off the resulting black-brown precipitate, it was washed with hexane, ethanol and acetone successively and dried under reduced pressure to obtain a near-infrared absorbing dye (A-NIR1) represented by the following chemical formula (17). rice field. 50 parts of the obtained near-infrared absorbing dye (A-NIR1), 500 parts of sodium chloride and 60 parts of diethylene glycol were placed in a gallon kneader made of stainless steel (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture is poured into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, dried at 80°C for a day and night, and pulverized. As a result, a fine near-infrared absorbing dye (A-NIR1) was obtained.

chemical formula (17)

(Near-infrared absorbing dye (A-NIR2))
40.0 parts of 1,8-diaminonaphthalene, 50.1 parts of 2-hydroxy-9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate are mixed with 400 parts of toluene and mixed in a nitrogen gas atmosphere. The mixture was heated and stirred at , and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, a dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the solution was stirred in a nitrogen gas atmosphere. The mixture was heated and stirred in the medium, and the reaction was carried out under reflux for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the resulting reaction mixture. After filtering off the resulting black-brown precipitate, it is washed with hexane, ethanol and acetone successively and dried under reduced pressure to obtain a near-infrared absorbing dye (A-NIR2) represented by the following chemical formula (18). rice field. A near-infrared absorbing dye (A-NIR2) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR2) in the same manner as for A-NIR1.

chemical formula (18)

(Near-infrared absorbing dye (A-NIR3))
In a reaction vessel, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), 178 parts of 2,3-dicyanonaphthalene and 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. with stirring 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 a compound of the following chemical formula (19).
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. To this solution, 10 parts of the compound of the following chemical formula (19) was gradually added, and the mixture was stirred at 90°C for 120 minutes. Then, this reaction solution is poured into 2000 parts of water, and the resulting precipitate is filtered, washed with water, dried, and near-infrared absorbing dye (A-NIR3) represented by the following chemical formula (20). got A near-infrared absorbing dye (A-NIR3) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR3) in the same manner as for A-NIR1.

(Near-infrared absorbing dye (A-NIR4))
A near-infrared absorbing dye (A-NIR4) represented by the following chemical formula (21) was obtained according to the description of International Publication No. 2019/058882. A near-infrared absorbing dye (A-NIR4) was obtained by miniaturizing the near-infrared absorbing dye (A-NIR4) in the same manner as A-NIR1.

chemical formula (21)

<Production of binder resin (B)>
(Alkali-soluble binder resin (B1-1) solution)
Put 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and heat to 120 ° C. while injecting nitrogen gas into the vessel. After heating, 10.4 parts of styrene (hereinafter referred to as St), 85.3 parts of glycidyl methacrylate (hereinafter referred to as GMA), 67.2 parts of dicyclopentanyl methacrylate (hereinafter referred to as DCPMA), and azobis were added from the dropping tube at the same temperature. A mixture of 1.0 parts of isobutyronitrile (hereinafter referred to as AIBN) was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 43.2 parts of acrylic acid (hereinafter referred to as AA), and the mixture was reacted at 120° C. for 5 hours. As a result, the epoxy group of GMA and the carboxyl group of AA were reacted to introduce a structural unit (b1-1) derived from the epoxy group-containing monomer (hereinafter referred to as GMA+AA).
Further, 60.8 parts of tetrahydrophthalic anhydride (THPA) and 0.5 parts of triethylamine were added and reacted at 120° C. for 4 hours. As a result, the hydroxyl group of GMA-AA and TPHA were esterified to introduce a structure (b1-2) (hereinafter referred to as GMA+AA+THPA) derived from a fatty acid anhydride-modified polybasic acid anhydride. After that, PGMAc was added so that the non-volatile content was 20% to prepare an alkali-soluble binder resin (B1-1) solution.

(Alkali-soluble binder resins (B1-2) to (B1-11),
Alkali-soluble binder resins (B1-2) to (B1-11) were synthesized by changing the raw materials, composition ratios, and amounts shown in Table 1, and adding PGMAc to increase the nonvolatile content to 20%. bottom. In addition, the numerical value in a table|surface is mol%.

(Alkali-soluble binder resin solution (Bb-1) having a structural unit having a blocked isocyanato group)
After putting 149.3 g of propylene glycol monomethyl ether into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, the mixture was stirred under nitrogen substitution and heated to 78°C. Next, 16.1 g of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenzu MOI-BP, manufactured by Showa Denko KK), 6.7 g of styrene, 28.2 g of dicyclopenta 11.2 g of 2,2'-azobis(2,4-dimethyl valeronitrile) (polymerization initiator) was added and dissolved in 62.8 g of propylene glycol monomethyl ether acetate, and was dropped into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 78° C. for 3 hours to carry out a copolymerization reaction to form a copolymer. After that, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20%, to obtain an alkali-soluble binder resin solution (Bb-1) having a structural unit having a blocked isocyanato group. The copolymer in the obtained polymer composition had a weight average molecular weight of 8,100 and an acid value of 80 KOHmg/g.

(Alkali-soluble binder resin solutions (Bb-2) to (Bb-4) having a structural unit having a blocked isocyanato group)
Except for using the raw materials listed in Table 1-2, a copolymerization reaction is performed under the same conditions as for the alkali-soluble binder resin solution (Bb-1) having a structural unit having a blocked isocyanato group, and a composition having a blocked isocyanato group is obtained. Alkali-soluble binder resin solutions (Bb-2 to 4) having units were obtained. Table 1-2 shows the weight average molecular weight and acid value of the copolymer in the resulting polymer composition. In Table 1, 2-[O-(1′-methylproprideneamino)carboxyamino]ethyl methacrylate is Showa Denko KK, Karenz MOI-BM), and malonic acid-2-[[ [2-Methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester is Karenz MOI-DEM manufactured by Showa Denko KK.

The ranges of the glass transition temperature (Tg) of the binder resins listed in Table 1 are as follows.
A: -50°C or higher and -10°C or lower B: -10°C or higher and 80°C or lower C: 80°C or higher and lower than 150°C D: -50°C or lower, or 150°C or higher

<Production of resin type dispersant (Z)>

(Basic resin type dispersant (ZB-1) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, and nitrogen was flowed. While stirring at 50° C. for 1 hour, 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 (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the nonvolatile content was measured. % or more, the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc is added and diluted so that the nonvolatile content is 30% by nonvolatile measurement, and a resin type dispersant (ZB-1) solution having an amine value per nonvolatile content of 57 mgKOH / g and a number average molecular weight of 4,500 (Mn) is added. Obtained.
(Acidic resin-type dispersant (ZA-1) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate are charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas is introduced. replaced with
The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by measuring the non-volatile content that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and heated at 100°C. Reacted for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. Resin-type dispersant (ZA-1) with a value of 70 mgKOH/g and a weight average molecular weight of 8,500
got

(Acidic resin-type dispersant (ZA-2) solution)
80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko), ETERNA COLLO XMA (Ube 20 parts of Kosan Co., Ltd.) and 100 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The inside of the reaction vessel is heated to 80° C., and a solution of 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol is added. and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N ( Hydroxyl value 112 mgKOH/g, manufactured by Kuraray Co., Ltd.)) 106 parts, trimellitic anhydride 33 parts, cyclohexanone 392 parts, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.40 parts as a catalyst was added and reacted at 100° C. 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. The nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain a resin type dispersant (ZA-2) liquid having an acid value of 94 mgKOH/g and a weight average molecular weight of 25,000.

(Acidic resin-type dispersant (ZA-3) solution)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, 0.01 part of mono-n-butyltin (IV) oxide was charged to each, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70°C, and 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate are charged. A solution prepared by dissolving 0.1 part of 2′-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added and reacted for 10 hours. After confirming that the polymerization had progressed by 95% by measuring the solid content, the reaction was terminated. After completion of the reaction, the non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and a resin type dispersant (ZA-
3) A liquid was obtained.

(Photocrosslinkable acidic resin type dispersant (ZAUV-1) solution)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of monobutyltin oxide as a catalyst in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. was charged and purged with nitrogen gas, followed by reaction at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80° C., 1.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 part of hydroquinone were charged, and the concentration of 2270 cm-1 based on the isocyanate group was measured by IR. The reaction was continued until disappearance of the peak was confirmed (third step). After confirming disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (ZAUV-1) solution with a non-volatile content of 30%. The resulting dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size It was filtered through a 1.0 μm filter to prepare Dispersion 1.
Finely divided pigment (A-R177): 11.0 parts Resin type dispersant (ZAUV-1): 30.0 parts Organic solvent (PGMAc): 59.0 parts

(Dispersions 2 to 31)
Dispersions 2 to 31 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Tables 2-1 and 2-2 were changed.

<Production of photosensitive coloring composition>
[Comparative Example 1]
(Photosensitive coloring composition 1)
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1
got
Dispersion 31: 40.91 parts Binder resin (Bb-4) solution: 10.09 parts Polymerizable compound (C-1): 4.50 parts Photopolymerization initiator (D-2): 0.30 parts Organic solvent (PGMAc): 44.20 parts

[Comparative Example 2]
(Photosensitive coloring composition 2)
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to prepare a photosensitive coloring composition 2
got
Dispersion 31: 40.91 parts Binder resin (Bb-4) solution: 10.04 parts Polymerizable compound (C-1): 4.50 parts Photopolymerization initiator (D-2): 0.30 parts Leveling agent (E-1): 1.00 parts Organic solvent (PGMAc): 43.25 parts

[Example 1]
(Photosensitive coloring composition 3)
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 3
got
Dispersion 31: 40.91 parts Binder resin (Bb-4) solution: 10.04 parts Polymerizable compound (C-1): 4.50 parts Photopolymerization initiator (D-1): 0.30 parts Leveling agent (E-1): 1.00 parts Organic solvent (PGMAc): 43.25 parts

[Examples 2 to 62]
(Photosensitive coloring compositions 4 to 64)
Photosensitive coloring composition 3 of Example 1, Tables 3-1 to Table 3-7 the raw materials described in Table 3-7, except that the amount was changed in the same manner as in Example 1 to prepare photosensitive coloring compositions 4 to 64. bottom.

The raw materials listed in Tables 3-1 to 3-7 are as follows.

[Polymerizable compound (C)]
C-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[Photoinitiator (D)]
(Oxime-based photopolymerization compounds other than general formulas (1) to (5))
D-2: IRGACURE OXE-02 (manufactured by BASF Japan, ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime))
(Oxime photopolymerizable compound (D1-1) represented by general formula (1))
D1-1-1: Compound D1-1-2 of chemical formula (1-1) above: Compound D1-1-3 of chemical formula (1-2) above: Compound D1- of chemical formula (1-3) above 1-4: The compound of the above chemical formula (1-4) (oxime-based photopolymerizable compound (D1-2) represented by general formula (2))
D1-2-1: Compound D1-2-2 of chemical formula (2-1) above: Compound D1-2-3 of chemical formula (2-2) above: Compound D1- of chemical formula (2-3) above 2-4: The compound of the above chemical formula (2-4) (oxime-based photopolymerizable compound (D1-3) represented by general formula (3))
D1-3-1: compound of the above chemical formula (3-1) D1-3-2: compound of the above chemical formula (3-2) D1-3-3: compound of the above chemical formula (3-3) (general Oxime-based photopolymerizable compound represented by formula (4) (D1-4))
D1-4-1: Compound D1-4-2 of chemical formula (4-1) above: Compound D1-4-3 of chemical formula (4-2) above: Compound D1- of chemical formula (4-3) above 4-4: The compound of the above chemical formula (4-4) (oxime-based photopolymerizable compound (D1-5) represented by general formula (5))
D1-5-5: compound of the above chemical formula (5-5) D1-5-6: compound of the above chemical formula (5-6) D1-5-7: compound of the above chemical formula (5-7)

[Leveling agent (E)]
E-1: A solution of 1 part of BYK-330 (manufactured by BYK-Chemie) dissolved in 99 parts of PGMAc E-2: A solution of 1 part of Megafac F-554 (manufactured by DIC) dissolved in 99 parts of PGMAc

[Organic solvent (Q)]
PGMAc: propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition>
The resulting photosensitive colored compositions 1 to 64 (Examples 1 to 62, Comparative Examples 1 and 2) were evaluated for tapered shape, solvent resistance, development stains, substrate adhesion, and development speed by the following methods. gone. Evaluation results are shown in Tables 4-1 to 4-5.

[Taper shape evaluation]
The resulting photosensitive coloring composition is applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying is 2.5 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed through a photomask with a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 100 mJ/cm ² using a high-pressure mercury lamp. After that, the substrate was subjected to spray development using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. at three levels of development time (30 seconds, 60 seconds, and 90 seconds), and then washed with deionized water. It was air-dried and heated in a clean oven at 90° C. for 30 minutes to obtain a substrate for adhesion evaluation. It was observed and evaluated using an electron microscope. The evaluation criteria are as follows, and 2 or more is practical.
3: Forward tapered shape with gentle cross section at development time of 30 seconds and 60 seconds 2: Reverse taper shape at either level of development time of 30 seconds or 60 seconds 1: Reverse taper shape at development time of 30 seconds or 60 seconds

[Solvent resistance evaluation]
The obtained photosensitive coloring composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) of 100 mm long×100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness would be 2.5 μm. and dried on a hot plate at 70° C. for 1 minute. Then, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet rays through a photomask having a square pattern of 100 μm square at an illumination intensity of 30 mW/cm ² and 100 mJ/cm ² . Furthermore, after cooling this substrate to room temperature, it was spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. for a development time of 40 seconds, washed with deionized water, and air-dried with clean air. Then, it was heated in a clean oven at 90° C. for 30 minutes to obtain a solvent resistance evaluation substrate. The square pattern portion of the substrate was immersed in propylene glycol monomethyl ether acetate, and evaluated by observing the appearance and calculating ΔEab. In addition, evaluation criteria are as follows, and 3 or more is practicable.
5: No change in appearance after 30 minutes of immersion, ΔEab is 5 or less 4: No change in appearance after 20 minutes of immersion, ΔEab is 5 or less 3: No change in appearance after 10 minutes of immersion, ΔEab is 5 or less 2: Immersion time is 5 No change in appearance after 3 minutes, ΔEab is 5 or less 1: No change in appearance after immersion for 3 minutes, ΔEab is 5 or less

[Development stain evaluation]
The obtained photosensitive coloring composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) of 100 mm long×100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness would be 2.5 μm. and dried on a hot plate at 70° C. for 1 minute. Then, it was exposed to ultraviolet light through a photomask having a stripe pattern of 100 μm width at an illumination intensity of 30 mW/cm ² and 100 mJ/cm ² using an extra-high pressure mercury lamp. Furthermore, after cooling this substrate to room temperature, it is spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. for a development time of 40 seconds, washed with deionized water, and air-dried with clean air. Then, a substrate for evaluation was obtained. On the photocured portion remaining after the development, a 5×5 cm area at the center of the substrate was observed with an optical microscope at a magnification of 50, and the portion where the color was locally changed was observed as a development stain. The evaluation criteria are as follows, and 3 or more is practical.
5: No development spots are observed in the entire photocured portion.
4: Development stains were observed in less than 10% of the area of the entire photocured portion as 100%.
3: Development stains were observed in 10% or more and less than 20% of the area of the entire photocured portion as 100%.
2: Development stains were observed in 20% or more and less than 50% of the area of the entire photocured portion as 100%.
1: Development stains were observed in 50% or more of the area of the entire photocured portion as 100%.

[Base material adhesion evaluation]
The resulting photosensitive coloring composition is applied to a glass substrate (Eagle 2000 manufactured by Corning) of 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying is 2.5 μm. and dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, it was exposed at an illumination intensity of 30 mW/cm ² and 100 mJ/cm ² using a high-pressure mercury lamp through a photomask having a stripe pattern with a width of 5 to 25 μm in increments of 5 μm. Thereafter, the substrate was developed by spraying with a potassium hydroxide solution (concentration: 0.04% by mass) at 23°C, washed with deionized water, air-dried with clean air, and heated in a clean oven at 90°C for 30 minutes. A substrate for adhesion evaluation was obtained. The spray development was carried out for the shortest time in which a pattern can be formed without leaving any development residue on the film with each photosensitive coloring composition, and this was taken as the appropriate development time.
A thin line pattern with a width of 5 to 25 μm among the patterns of the adhesion evaluation substrate was observed with an optical microscope to confirm the minimum line width of the remaining thin line pattern. The evaluation criteria are as follows, and 3 or more is practical.
5: Fine lines of 10 μm or less remain.
4: Fine lines exceeding 10 μm and 15 μm or less remain.
3: Fine lines exceeding 15 μm and 20 μm or less remain.
2: Fine lines exceeding 20 μm and 25 μm or less remain.
1: Fine lines do not remain.

[Development speed evaluation]
The photosensitive coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness would be 2.5 μm, and dried at 70° C. for 1 minute. 2 ml of an aqueous solution of potassium hydroxide at 23° C. (concentration: 0.04% by mass) is added dropwise to the coating film, and the time until the coating thickness dissolves is measured, and the development speed of the photosensitive coloring composition is measured. evaluated. The evaluation rank is as follows, and 3 or more is practical.
5: Less than 25 seconds 4: 25 seconds or more, less than 35 seconds 3: 35 seconds or more, less than 45 seconds 2: 45 seconds or more, less than 55 seconds 1: 55 seconds or more

10 image display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 orientation layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 orientation layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal 200 solid-state imaging device 201 Solid-state imaging device 202 Imaging unit 203 Cover glass 204 Spacer 205 Laminated substrate 206 Chip substrate 207 Circuit substrate 208 Electrode pad 209 External connection terminal 210 Through electrode 211 Lens layer 212 Lens material 213 Support 214 Hardened film 215 Hardened film 300 Infrared sensor 310 Solid-state imaging device 311 Infrared cut filter 312 Color filter 313 Infrared absorption transmission filter 314 Resin film 315 Microlens 316 Flat film

Claims (13)

A dye (A), a binder resin (B) (however, a resin that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, a hydroxyl group of a compound having a hydroxyl group, A resin having a side chain obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of a tetracarboxylic dianhydride, and a vinyl polymer having one hydroxyl group at one end to the hydroxyl group of the tricarboxylic anhydride), a polymerizable compound (C), a photopolymerization initiator (D), an acidic resin-type dispersant (ZA), and a leveling agent (E) for color filters Or a photosensitive coloring composition for an optical filter,
The binder resin (B) contains an alkali-soluble binder resin (Bb) having a structural unit having a blocked isocyanato group in which the blocking agent is diethyl malonate,
The photopolymerization initiator (D) is an O-acyl oxime ester-based light represented by the following general formula (1), general formula (2), general formula (3), general formula (4) or general formula (5) A photosensitive coloring composition for a color filter or an optical filter, which is a polymerization initiator (D1).

General formula (1):
[In general formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R ³ represents —COR ⁵ , a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. ^R5 represents a phenyl group which may have a substituent. R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group, cyclic alkyl group, acyl group, and phenyl group of R ¹ to R ⁴ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. may The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with another substituent R ⁶ . ^R6 represents a halogen atom, fluorine atom, alkyl group, cyclic alkyl group, acyl group, nitro group, sulfo group and phenyl group. ]

General formula (2):
[In general formula (2), R ¹ and R ² each independently have a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic substituent having 3 to 20 carbon atoms, represents an alkyl group or a phenyl group. R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group or a sulfo group. The alkyl group, cyclic alkyl group, acyl group and phenyl group of R ¹ to R ³ above are substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. may R ⁴ is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the aryl group or arylalkyl group represented by R ⁴ may be further substituted with R ₂₁ , —OR ₂₁ , —COR ₂₁ , hydroxyl group, nitro group, cyano group, halogen atom, or —COOR ₂₁ , R ₂₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 _carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the alkyl group, aryl group, A hydrogen atom of the arylalkyl group may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁴ may be further substituted with other substituents. ]

General formula (3):
[In general formula (3), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. indicates R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. The alkyl group, acyl group and phenyl group of R ¹ to R ³ may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. ^R4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or ^-COR6 . R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. The hydrogen atoms of the substituents in R ¹ to R ⁶ may be further substituted with other substituents. ]

General formula (4):
[In general formula (4), R ¹ and R ² are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. indicates R ³ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group; show. ^R4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group optionally interrupted by a hydroxyl group. The alkyl group, acyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms and a phenyl group. The hydrogen atoms of the substituents in R ¹ to R ⁵ may be further substituted with other substituents. ]

general formula (5)
[In general formula (5), R ₁ and R ₂ each independently represent R ₁₁ or -COR ₁₁ ,
R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, _an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; The alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl,
R ₃ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and is represented by R ₃ The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl, and the aryl group, arylalkyl group or heterocyclic group represented by _R3 The hydrogen atoms of are further R ₂₁ , —OR ₂₁ , —COR ₂₁ , —SR ₂₁ , —NR ₂₂ R ₂₃ , —CONR ₂₂ R ₂₃ , —NR ₂₂ —OR ₂₃ , —NCOR ₂₂ —OCOR ₂₃ , —NR ₂₂ optionally substituted with COR ₂₁ , —OCOR ₂₁ , —SCOR ₂₁ , —OCSR ₂₁ , —COSR ₂₁ , —CSOR ₂₁ , a hydroxyl group, a nitro group, a cyano group, a halogen atom, or —COOR ₂₁ ;
R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 4 to 20 carbon atoms. The hydrogen atom of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ is further a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or may be substituted with a carboxyl group, and the alkylene portion of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by R ₂₁ , R ₂₂ and R ₂₃ may be -O-, -S-, - adjacent oxygen atoms by COO-, -OCO-, -NR ₂₄ -, -NR ₂₄ CO-, -NR ₂₄ COO-, -OCONR ₂₄ -, -SCO-, -COS-, -OCS- or -CSO-; It may be interrupted 1 to 5 times under no conditions,
R ₂₄ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, _an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; The alkyl moiety of the represented alkyl group, aryl group, arylalkyl group or heterocyclic group may have a branched side chain or may be a cyclic alkyl,
_R4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom; n represents 0 or 1; ] 2. The photosensitive coloring composition for color filters or optical filters according to claim 1, wherein the leveling agent (E) contains one of a silicone surfactant and a fluorosurfactant. The binder resin (B) further contains an alkali-soluble binder resin (B1) having a polystyrene-equivalent weight average molecular weight of 5,000 or more and less than 50,000 (excluding the case where it is an alkali-soluble binder resin (Bb)), The photosensitive coloring composition for color filters or optical filters according to claim 1 or 2. 4. The photosensitive coloring composition for color filters or optical filters according to claim 3, wherein the alkali-soluble binder resin (B1) contains a structural unit (b3) having an aliphatic ring group. 5. The color filter or optical filter according to claim 4, wherein the structural unit (b3) having an aliphatic ring group in the alkali-soluble binder resin (B1) has a ring represented by formula (b31) or formula (b32). A photosensitive coloring composition.

The photosensitive coloring for color filters or optical filters according to any one of claims 3 to 5, wherein the alkali-soluble binder resin (B1) further contains a structure (b1-2) derived from a polybasic acid anhydride. Composition. The photosensitive coloring composition for a color filter or an optical filter according to any one of claims 1 to 6, wherein the acidic resin-type dispersant (ZA) comprises a photocrosslinkable acidic resin-type dispersant (ZAUV-1). thing. A cured film, which is a cured product of the photosensitive coloring composition for a color filter or an optical filter according to any one of claims 1 to 7. A color filter comprising the cured film according to claim 8 . An optical filter comprising the cured film according to claim 8 . An image display device comprising the cured film according to claim 8 . A solid-state imaging device comprising the cured film according to claim 8 . An infrared sensor comprising the cured film according to claim 8 .

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