JP7613832B2 - Cyan photosensitive coloring composition for color filters, its manufacturing method, color filter, and solid-state imaging device - Google Patents

Description

The present invention relates to a coloring composition and a color filter used in the manufacture of color filters for use in solid-state imaging devices and the like.

In solid-state imaging devices such as C-MOS (Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), and the like, color filters having additive primary color filter segments of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) are generally arranged on the light receiving element to perform color separation. On the other hand, color filters having filter segments of cyan, magenta, and yellow (CMY), which correspond to the complementary colors of red, green, and blue, have been attracting attention in recent years because they provide higher sensitivity than primary color filters. Complementary color filters are often used in video cameras and the like that do not easily use auxiliary light sources such as flashes, and are considered to contribute to high sensitivity, especially in nighttime photography.
Therefore, in recent years, there has been an increasing demand for color filters used in solid-state imaging devices to have high transmittance, i.e., high brightness and high reliability.

Color filters are manufactured using a photosensitive coloring composition that contains a colorant and a curable compound. Recently, the use of aluminum phthalocyanine pigments has also been considered (see Patent Documents 1 to 3).

JP 2015-045706 A JP 2014-199308 A JP 2009-221376 A

Cyan generally has the property of transmitting light with wavelengths between 400nm and 600nm, and blocking light above 600nm. In contrast, aluminum phthalocyanine pigments have superior cyan color characteristics compared to other phthalocyanine compounds, and the development of color filters with cyan pixels is being considered.

However, coloring compositions and photosensitive compositions containing these aluminum phthalocyanine pigments have problems such as aggregation of pigment particles due to poor dispersibility and poor stability over time. Furthermore, when a dye derivative is added to improve dispersibility, while the dispersibility is improved, there is also a problem that the transmittance in the region of 400 to 500 nm decreases, resulting in poor color characteristics as a cyan color.

The problem that the present invention aims to solve is to provide a cyan photosensitive coloring composition for a color filter for a solid-state imaging device, which has excellent color characteristics (transmittance) for cyan and good stability over time, and a color filter.

The present inventors have considered the above problems and conducted extensive research to solve them, leading to the present invention.
That is, the present invention provides a cyan photosensitive coloring composition for a color filter for a solid-state imaging device, comprising a colorant, a resin-type dispersant, a binder resin, a polymerizable compound, a photopolymerization initiator, and an organic solvent,
The present invention relates to a cyan photosensitive coloring composition for a color filter for a solid-state imaging device, characterized in that the colorant contains a phthalocyanine pigment represented by the following general formula (1) and a zinc phthalocyanine compound:

General formula (1)

In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
^R1 and ^R2 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or ^-OR3 , and ^R1 and ^R2 may be bonded to each other to form a ring. ^R3 is an alkyl group which may have a substituent, or an aryl group which may have a substituent.]

The present invention also relates to the above-mentioned cyan photosensitive coloring composition for color filters for solid-state imaging devices, characterized in that the zinc phthalocyanine compound contains a halogenated zinc phthalocyanine pigment.

The present invention also relates to a cyan photosensitive coloring composition for color filters for solid-state imaging devices, characterized in that the cyan coloring composition for color filters for solid-state imaging devices contains a co-dispersion of a phthalocyanine pigment represented by general formula (1) and a zinc phthalocyanine compound.

The present invention also relates to the photosensitive coloring composition for color filters, characterized in that the resin-type dispersant contains a basic resin-type dispersant having an amine value of 10 to 300 mg KOH/g and a resin-type dispersant having a carboxyl group.

The present invention also relates to a cyan photosensitive coloring composition for color filters for solid-state imaging devices according to any one of claims 1 to 4, in which, when a coating film formed from the cyan photosensitive coloring composition for color filters for solid-state imaging devices has a thickness of 0.5 μm, the coating film has a light transmittance of 70% or more at wavelengths of 400 to 460 nm, an average light transmittance of 80% or more at wavelengths of 480 to 550 nm, and an average light transmittance of 20% or less at wavelengths of 620 to 680 nm.

The present invention also relates to a method for producing a cyan photosensitive coloring composition for a color filter for a solid-state imaging device, which comprises co-dispersing a phthalocyanine pigment represented by the following general formula (1) and a zinc phthalocyanine compound in a binder resin using a media-type wet disperser.

General formula (1)

In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
^R1 and ^R2 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or ^-OR3 , and ^R1 and ^R2 may be bonded to each other to form a ring. ^R3 is an alkyl group which may have a substituent, or an aryl group which may have a substituent.]

The present invention also relates to a filter segment formed from the above-mentioned cyan photosensitive coloring composition for a color filter for a solid-state imaging device.

The present invention also relates to a color filter for a solid-state imaging device, characterized in that the above-mentioned filter segment is provided on a substrate.

The present invention also relates to a solid-state imaging device that is equipped with the above-mentioned color filter for solid-state imaging devices.

The present invention provides a cyan photosensitive coloring composition for color filters for solid-state imaging devices that has excellent color characteristics (transmittance) for cyan and good stability over time, and a color filter.

Hereinafter, embodiments of the present invention will be described in detail.
In this specification, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refer to "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. In addition, "C.I." in this specification means Color Index (C.I.).

<Coloring Agent>
The cyan photosensitive coloring composition for a color filter for a solid-state imaging device of the present invention is a coloring composition containing at least a colorant, a resin-type dispersant, a binder resin, and an organic solvent, and is characterized in that the colorant contains a phthalocyanine pigment represented by the following general formula (1) (hereinafter, sometimes referred to as a "specific phthalocyanine dye") and a zinc phthalocyanine compound. By using the phthalocyanine dye in combination, a cyan color filter having extremely small absorption in the range of 450 nm to 550 nm and excellent cyan spectral characteristics can be formed.

(Phthalocyanine pigment represented by general formula (1))
General formula (1)

[In general formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ¹ and R ² each independently represent a hydrogen atom, a hydroxy group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or -OR ³ , and R ¹ and R ² may be bonded to each other to form a ring. R ³ is an alkyl group which may have a substituent, or an aryl group which may have a substituent.]

Examples of the halogen atom in A ¹ to A ¹⁶ include fluorine, chlorine, bromine, and iodine.

The alkyl group which may have a substituent in A ¹ to A ¹⁶ and R ¹ to R ³ includes a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms. The "substituent" includes a halogen atom such as chlorine, fluorine or bromine, an alkoxy group such as a methoxy group, a nitro group, etc. Specific examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-nitropropyl group, an isopropyl group, an isopentyl group, a 2-ethylhexyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a bornyl group, and a 4-decylcyclohexyl group.

The aryl group which may have a substituent in A ¹ to A ¹⁶ and R ¹ to R ³ includes a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms. The "substituent" includes a halogen atom such as chlorine, fluorine, or bromine, an alkyl group, an alkoxy group such as a methoxy group, an amino group, and a nitro group. Specific examples include a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-methoxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

In terms of dispersibility and color characteristics, it is preferable that A ¹ to A ¹⁶ of the specific phthalocyanine colorant usable in the cyan photosensitive coloring composition for color filters for solid-state imaging devices of the present invention are any of hydrogen atoms, halogen atoms, and methyl groups. More preferably, A ¹ to A ¹⁶ are all hydrogen atoms.

Furthermore, as for the specific phthalocyanine dye that can be used in the cyan photosensitive coloring composition for color filters for solid-state imaging devices of the present invention, from the viewpoint of dispersibility and color characteristics, it is preferable that at least one of R ¹ and R ² is an aryl group that may have a substituent, or an aryloxy group that may have a substituent (-OR ³ , where R ³ is an aryl group that may have a substituent). More preferably, R ¹ and R ² are an aryl group that may have a substituent, or an aryloxy group that may have a substituent (-OR ³ , where R ³ is an aryl group that may have a substituent), and even more preferably, R ¹ and R ² are a phenyl group or a phenoxy group, which are preferable because they have excellent transmittance.

The content of the phthalocyanine pigment represented by general formula (1) is preferably 50 parts by mass or more per 100 parts by mass of the colorant, and more preferably 70 parts by mass or more from the viewpoint of the color characteristics of the cyan color.

(Zinc phthalocyanine compound)
The cyan photosensitive coloring composition for a color filter for a solid-state imaging device of the present invention is characterized in that it contains a zinc phthalocyanine compound together with the phthalocyanine pigment represented by the general formula (1). The zinc phthalocyanine compound includes a zinc phthalocyanine compound represented by the following general formula (2).

(Zinc phthalocyanine compound represented by general formula (2))
General formula (2)

[In general formula (2), 0 to 16 L's can be present in one phthalocyanine skeleton, and each L independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a basic functional group, or an acidic functional group.]

Halogen atoms in L include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group in L which may have a substituent include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Examples of the "substituent" include halogen atoms such as chlorine, fluorine and bromine, alkoxy groups such as methoxy groups, and nitro groups. Specific examples include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2-ethoxyethyl, 2-butoxyethyl, 2,2,3,3-tetrafluoropropyl, 2-nitropropyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, tert-octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, bornyl, and 4-decylcyclohexyl.

The aryl group in L, which may have a substituent, includes a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms. Examples of the "substituent" include halogen atoms such as chlorine, fluorine, and bromine, alkyl groups, alkoxy groups such as methoxy groups, amino groups, and nitro groups. Specific examples include, but are not limited to, phenyl groups, naphthyl groups, anthranyl groups, p-methylphenyl groups, p-bromophenyl groups, p-nitrophenyl groups, p-methoxyphenyl groups, 2,4-dichlorophenyl groups, pentafluorophenyl groups, 2-aminophenyl groups, 2-methyl-4-chlorophenyl groups, 4-methoxy-1-naphthyl groups, 6-methyl-2-naphthyl groups, 4,5,8-trichloro-2-naphthyl groups, anthraquinonyl groups, and 2-aminoanthraquinonyl groups.

The basic functional group in L refers to a functional group containing a nitrogen atom. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-05-009469, JP-B-5962069, etc. are not limited thereto. These can be used alone or in a mixture of two or more types.

The acidic functional group in L includes a sulfo group, a carboxy group, a hydroxy group, and a phenol group.

(Halogenated zinc phthalocyanine pigment)
The coloring composition for color filters of the present invention preferably contains a halogenated zinc phthalocyanine pigment as the phthalocyanine pigment represented by the general formula (2). Examples of the "halogen" include fluorine, bromine, chlorine, and iodine, and bromine and chlorine are preferred. Examples of the halogenated zinc phthalocyanine pigment include, but are not limited to, zinc phthalocyanine pigments described in, for example, C.I. Pigment Green 58, 59, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and WO 2015/118720 pamphlet.

(Other colorants)
The cyan photosensitive coloring composition for a color filter for a solid-state imaging device of the present invention may contain other colorants within a range that does not impair the effects of the present invention, for the purpose of adjusting chromaticity, etc. Examples of other colorants include, but are not limited to, a green dye and a blue dye.

The green colorant includes a green pigment or a green dye.
Examples of green pigments include, but are not limited to, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, and 55.

Examples of green dyes include C.I. solvent dyes such as C.I. Solvent Green 1, 4, 5, 7, 34, and 35, C.I. acid dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, and 109, C.I. direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82, and C.I. mordant dyes such as C.I. Mordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, and 53, but are not limited thereto.

Blue dyes include, but are not limited to, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, and 64.

(Fine particle size of colorant)
The colorant used in the photosensitive coloring composition of the present invention can be suitably used as a colorant for color filters by, if necessary, subjecting the colorant particles to fine processing such as salt milling in order to obtain high light transmittance. The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to enhance dispersibility in the pigment carrier. In addition, in order to obtain a filter segment with high contrast, it is preferably 80 nm or less. The particularly preferred range is 20 to 60 nm.

Salt milling is a process in which a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the colorant is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the colorant, a colorant can be obtained that has a very fine volume average primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

Sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

The water-soluble organic solvent is a solvent that moistens the colorant and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is mixed) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, from the viewpoint of safety, a solvent with a high boiling point of 120°C or higher is preferable. Examples of such solvents include 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, etc. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

When the colorant is subjected to salt milling, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above-mentioned water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by mass, based on the total mass of the colorant (100% by mass).

<Method for producing colored composition for color filters (pigment dispersion)>
The coloring composition of the present invention can be produced by finely dispersing the colorant in a pigment carrier made of a binder resin and/or an organic solvent, preferably together with a dispersion aid, using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (pigment dispersion). In particular, it is preferable to carry out bead dispersion using zirconium oxide or inorganic glass, and beads of different diameters may be used in this case. In addition, after carrying out the above bead dispersion, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust, using a means such as a centrifuge with a gravitational acceleration of 3000 to 25000 G, a sintered filter, or a membrane filter. In this case, the phthalocyanine pigment represented by the general formula (1), the zinc phthalocyanine compound, and other colorants may be dispersed simultaneously in the pigment carrier, or they may be dispersed separately in the pigment carrier and then mixed. However, from the viewpoint of viscosity stability and contrast ratio, it is more preferable to use a co-dispersion in which the phthalocyanine pigment represented by the general formula (1) and the zinc phthalocyanine compound are dispersed simultaneously in the pigment carrier.

(Covariance)
In the present invention, the method for producing the coloring composition is preferably to co-disperse the phthalocyanine pigment represented by the general formula (1) and the zinc phthalocyanine compound in the binder resin using a media-type wet disperser. The term "co-dispersion" refers to mixing two or more pigments and dispersing them under the same conditions. By co-dispersion, the pigment particles can be finely dispersed and dispersed well, and a coloring composition for color filters having excellent dispersion stability after dispersion can be prepared.

The co-dispersion method can be carried out, for example, by mixing at least two types of pigments with a dispersant in advance, pre-dispersing them using a homogenizer or the like, and dispersing them using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Of these, it is preferable to co-disperse them using a media-type wet disperser.

In the present invention, it is even more preferable to include at least one dispersant when carrying out co-dispersion, since this can improve the dispersibility of the pigment.

<Resin-type dispersant>
The resin-type dispersant has a colorant-affinity site that has the property of adsorbing to the colorant and a site that is compatible with the pigment carrier, and functions to adsorb to the colorant and stabilize the dispersion of the colorant in the pigment carrier. Specifically, as the resin type dispersant, polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, poly (lower alkylene imine) and free carboxyl group-containing polyesters formed by reaction with amides and their salts, oil-based dispersants such as amides and their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins such as polyvinylpyrrolidone and water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used, which can be used alone or in a mixture of two or more, but are not necessarily limited to these.

Commercially available resin-type dispersants include DISPERBYK-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 21 64, or Anti-TeRRa-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by Lubrizol Japan Co., Ltd. SOLSPERSE-3000, 9000, 11200, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 280 00, 31845, 32000, 32500, 32550, 3300, 33500, 32600, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 56000, 55000, 7100, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080 manufactured by BASF , 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the resin-type dispersant is preferably 0.1 to 150 parts by mass, and more preferably 30 to 100 parts by mass, per 100 parts by mass of the colorant. If the content of the resin-type dispersant is less than 0.1 parts by mass, it is difficult to obtain the effect of adding it, and if the content is more than 150 parts by mass, the excess dispersant may affect the dispersion.

(Basic resin type dispersant)
The coloring composition for color filters of the present invention preferably contains a basic resin-type dispersant having an amine value of 10 to 300 mgKOH/g among resin-type dispersants. More preferably, it is 50 to 300 mgKOH/g. When a basic resin-type dispersant having an amine value in this range is used, it is sufficiently adsorbed to the pigment by adsorption or reaction with the acidic component in the pigment carrier, resulting in good dispersion and excellent dispersion stability. Since the halogenated zinc phthalocyanine pigment, which is an acidic pigment, is adsorbed to the pigment surface of the specific aluminum phthalocyanine pigment, which is a neutral pigment, a coloring composition for color filters having excellent dispersibility and dispersion stability can be obtained by using a basic resin-type dispersant having a high amine value as the resin-type dispersant used during dispersion.

The number average molecular weight of the basic resin-type dispersant used in the present invention is preferably 500 to 50,000, and more preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when a solvent is used are small, making it difficult to prevent pigment aggregation and causing the viscosity of the dispersion to increase. Furthermore, if the number average molecular weight is 50,000 or more, the amount of resin required for dispersion increases, which may lead to a decrease in the pigment concentration in the coating film.

Basic resin-type dispersants with an amine value of 10 to 300 mgKOH/g can be of various types, such as vinyl, urethane, polyester, polyether, or polyamide resins, but vinyl monomer copolymer types are preferred because they are easy to design and have excellent resistance to various factors. Specifically, copolymer resins of N,N-disubstituted amino group-containing vinyl monomer units, alkyl (meth)acrylate monomer units, and other vinyl monomer units are preferred.

Examples of N,N-disubstituted amino group-containing vinyl monomer units include, but are not limited to, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, and N,N-diethylaminoethyl (meth)acrylamide. These monomer units are adsorbed to the pigment as basic group-containing monomer units.

Examples of alkyl (meth)acrylate monomer units include, but are not limited to, (meth)acrylic esters obtained by reacting unsaturated monocarboxylic acids such as 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, or lauryl (meth)acrylate with alkyl alcohols having 1 to 18 carbon atoms. These monomer units act as pigment carrier affinity groups.

Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth)acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, and benzyl (meth)acrylate, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and polyethylene glycol (meth)acrylate, amide group-containing vinyl monomers such as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, and diacetone acrylamide, N-methylol (meth)acrylamide, and dimethylol (meth)acrylamide, and Examples of suitable vinyl monomers include vinyl monomers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and other vinyl fatty acids such as vinyl acetate and vinyl propionate. These are not necessarily limited to the above and may be used according to the intended purpose.

Other examples include comb-shaped basic resin-type dispersants in which a polymer having a primary amino group-containing monomer unit such as allylamine, or polyethyleneimine, polyethylenepolyamine, polyxylylenepoly(hydroxypropylene)polyamine, or poly(aminomethylated) epoxy resin is modified with a polyester resin, an acrylic resin, or a polyether resin.

Commercially available examples of such preferred basic resin-type dispersants include DISPERBYK161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050, 2150, 2163, 2164, and BYK-LPN6919 from BYK Japan Co., Ltd., and SOLSPERSE11200 from Lubrizol Japan Co., Ltd. , 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100, EFKA4300, 4330, 4046, 4060, 4080 from BASF, etc.

(Resin-type dispersant with carboxyl groups)

In the photosensitive coloring composition of the present invention, a resin-type dispersant having a carboxyl group can be suitably used. The shape of the resin-type dispersant having a carboxyl group includes a straight-chain resin-type dispersant and a comb-shaped resin-type dispersant.

[Comb-shaped resin-type dispersant 1 having a carboxyl group]
The comb-shaped resin-type dispersant 1 having a carboxyl group can be produced by known methods such as those described in WO2008/007776, JP2008-029901A, and JP2009-155406A.
For example, the resin-type dispersant is a reaction product between the hydroxyl group of a polymer having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride, or the resin-type dispersant is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride.

[Comb-shaped resin-type dispersant 2 having a carboxyl group]
The comb-shaped resin-type dispersant 2 having a carboxyl group can be produced by known methods such as those described in WO2008/007776, JP2009-155406A, JP2010-185934A, and JP2011-157416A.
For example, a resin-type dispersant is obtained by reacting, in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, a resin-type dispersant having a side chain formed by polymerizing an ethylenically unsaturated monomer having a thermal crosslinking group such as a hydroxyl group, a t-butyl group or an oxetane skeleton, or a blocked isocyanate, and other components, and further an ethylenically unsaturated monomer having an isocyanate group on the hydroxyl group in the side chain.

[Carboxyl group-containing linear resin-type dispersant 3]
The linear resin-type dispersant 3 having a carboxyl group can be produced by known methods such as those described in JP 2009-251481 A, JP 2007-23195 A, JP 1996-143651 A, etc. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic acid anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end as a raw material.

[Tetracarboxylic acid anhydride]
Examples of the tetracarboxylic dianhydride used in the present invention include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and the like. tetracarboxylic 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'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, Examples of aromatic tetracarboxylic acid dianhydrides include aromatic tetracarboxylic acid dianhydrides such as 3,4-diphenylphthalic 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, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

The tetracarboxylic dianhydrides used in the present invention are not limited to the compounds exemplified above, and may have any structure as long as they have two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydrides form a dispersant having two carboxyl groups per polyester unit by reacting with polyol, and are therefore preferred as components of the dispersant of the present invention from the viewpoint of pigment adsorption.

Furthermore, from the viewpoint of adsorption to colorants, aromatic tetracarboxylic dianhydrides are preferably used in the present invention, and more preferably, tetracarboxylic dianhydrides having two or more aromatic rings. Aromatic carboxylic acids have a higher pigment adsorption ability than aliphatic carboxylic acids, and furthermore, carboxylic acids having two or more aromatic rings have a skeleton suitable for pigment adsorption and also have high heat resistance.

[Tricarboxylic acid anhydride]
Examples of tricarboxylic anhydrides include aromatic tricarboxylic anhydrides such as benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (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, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. In terms of adsorption to pigments, aromatic tricarboxylic anhydrides are preferred to aliphatic carboxylic acids for use in the present invention.

The mass ratio of the basic resin-type dispersant to the resin-type dispersant having a carboxyl group among all the resin-type dispersants in the photosensitive composition of the present invention is preferably basic resin-type dispersant: resin-type dispersant having a carboxyl group=9:1 to 1:9, and more preferably basic resin-type dispersant: resin-type dispersant having a carboxyl group=7:3 to 3:7.

<Binder resin>
The binder resin disperses colorants such as pigments and dyes, particularly the phthalocyanine pigment represented by the general formula (1) and the zinc phthalocyanine compound, and examples of the binder resin include thermoplastic resins and thermosetting resins.

The binder resin is preferably a resin with a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable color resist material, it is preferable to use an alkali-soluble vinyl resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. In addition, to further improve photosensitivity and solvent resistance, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development type resist for color filters, no foreign matter is generated in the coating film after the colorant is applied, and the stability of the colorant in the resist material is improved, which is preferable. When a straight-chain resin without an ethylenically unsaturated double bond in the side chain is used, the colorant is less likely to be trapped by the resin in a liquid in which the resin and the colorant are mixed, and the colorant components are more likely to aggregate and precipitate due to the degree of freedom. However, by using an active energy ray curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is more likely to be trapped by the resin in a liquid in which the resin and the colorant are mixed, so that in a solvent resistance test, the pigment is less likely to be eluted and the colorant components are less likely to aggregate and precipitate. Furthermore, when a film is formed by exposure to active energy rays, the resin is three-dimensionally crosslinked, which fixes the colorant molecules, and it is presumed that the colorant components are less likely to aggregate and precipitate even if the solvent is removed in the subsequent development process.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, and more preferably in the range of 10,000 to 80,000, in order to disperse the colorant favorably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

The weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene equivalent molecular weights measured using an HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two TSK-GEL SUPER HZM-N columns connected in series, and THF as the solvent.

When the binder resin is used as a photosensitive coloring composition for color filters, from the viewpoint of pigment dispersibility, penetration, developability, and heat resistance, the balance between the carboxyl groups that act as colorant adsorption groups and alkali-soluble groups during development, and the aliphatic and aromatic groups that act as affinity groups for the pigment carrier and solvent is important for the pigment dispersibility, penetration, developability, and durability, and it is preferable to use a resin with an acid value of 20 to 300 mgKOH/g. If the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value exceeds 300 mgKOH/g, no fine pattern will remain.

The binder resin is preferably used in an amount of 30 parts by mass or more per 100 parts by mass of the total colorant, since it has good film-forming properties and various resistances, and is preferably used in an amount of 500 parts by mass or less, since it has a high colorant concentration and can express good color characteristics.

(Thermoplastic resin)
Examples of thermoplastic resins used for the binder resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes (HDPE, LDPE), polybutadiene, and polyimide resins. Of these, it is preferable to use acrylic resins.

Examples of vinyl-based alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include resins having acidic groups such as carboxyl groups and sulfonic groups. Specific examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, are preferably used because of their high heat resistance and transparency.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds have been introduced by the following methods (a) and (b).

[Method (a)]
Method (a) can be exemplified by a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and then a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an unsaturated ethylenic double bond, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

As a method similar to method (a), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is added to some of the side chain carboxyl groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
Method (b) includes a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. These may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, etc., may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin used as the binder resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, cardo resin, and phenol resin.

Thermosetting resins may be low molecular weight compounds such as epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenolic compounds, but the present invention is not limited thereto. By including such thermosetting resins, the resin reacts when the filter segments are baked, increasing the crosslink density of the coating film, improving heat resistance, and suppressing pigment aggregation when the filter segments are baked. Among these, epoxy resins, cardo resins, and melamine resins are preferred.

<Organic Solvent>
The colored composition of the present invention contains an organic solvent in order to facilitate the formation of a filter segment by dissolving the colorant sufficiently in a monomer, resin, etc., and applying the resulting solution to a substrate such as a glass substrate so as to give a dry film thickness of 0.2 to 5 μm.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, ethanol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol 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 glycerol 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 Examples of the organic solvent include ethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. These organic solvents can be used alone or in combination of two or more.

Among these, it is preferable to use glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone, because these have good dispersibility and penetration of the colorant and good applicability of the coloring composition.

The organic solvent is preferably used in an amount of 500 to 4,000 parts by weight per 100 parts by weight of the total weight of the colorant, since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of filter segments with the desired uniform thickness.

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

<Polymerizable Compound>
The photosensitive coloring composition of the present invention contains a polymerizable compound. The polymerizable compound includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene Pyrene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate 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, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane acrylate, and various acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, and the like, but are not necessarily limited thereto.

Commercially available products of these include 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, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, and M-32 manufactured by Toagosei Co., Ltd. 1, 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, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd. can be preferably used.

(Polymerizable compound having an acid group)
The polymerizable compound in the present invention may contain a photopolymerizable compound having an acid group. By using a photopolymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is subjected to alkaline development, the solubility of the formed coating film in an alkaline developer can be increased, and the development speed can be improved and the residue can be reduced. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Examples of photopolymerizable compounds having an acid group include esters of polyhydric alcohols and (meth)acrylic acid, poly(meth)acrylates containing free hydroxyl groups, and dicarboxylic acids; esters of polycarboxylic acids and monohydroxyalkyl (meth)acrylates. Specific examples include monoesters containing free carboxyl groups of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid); Examples include free carboxyl group-containing oligoesters of tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

As commercially available products, Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd. can be suitably used.

(Polymerizable compound having a urethane bond)
The photopolymerizable compound in the present invention may contain a photopolymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. By containing a photopolymerizable compound having a urethane bond, it is possible to suppress precipitation of the coloring material when the formed coating film is heated, and to improve the solvent resistance and adhesion to the substrate.

Examples of polymerizable compounds having a urethane bond include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting the alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, etc., but the effects of the present invention are not limited to these.

In addition, examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc., but the effects of the present invention are not limited to these.

Suitable commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM, UA-6LPA, UA-10HA, UA-10PA, UA-1100H, UA-15HA, UA-53H, UA-33H, and UA-7100 manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., but the effects of the present invention are not limited to these.

The above photopolymerizable compounds can be used alone or in a mixture of two or more in any ratio as required.

The amount of the photopolymerizable compound is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass), and more preferably 2 to 40 parts by mass from the viewpoints of photocurability and developability.

<Photopolymerization initiator>
The coloring composition of the present invention can be prepared in the form of a solvent-developable or alkali-developable photosensitive coloring composition by adding a photopolymerization initiator to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method.

Examples of the photopolymerization initiator (G) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, and benzoin ethyl ether. benzoin compounds such as benzoyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- triazine-based compounds such as bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; oxime ester compounds such as octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, or 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, but the effects of the present invention are not limited to these.
These photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as required.

Commercially available products include acetophenone compounds, all manufactured by IGM Resins, such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and phosphine compounds, all manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad "TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), etc.

In the present invention, it is preferable to contain an oxime ester compound among these.

(Oxime ester compounds)
In the oxime ester compound, the N-O bond of the oxime is cleaved by absorbing ultraviolet light, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film decreases, and the degree of curing of the coating film may decrease, but oxime ester compounds are preferably used because they have high quantum efficiency. Oxime ester photopolymerization initiators represented by general formula (5) are more preferred.

(Oxime ester photopolymerization initiator represented by general formula (3))
General formula (3)

In general formula (5),
Y ¹ is a hydrogen atom, or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, each of which may have a substituent;
^Y2 is a hydrogen atom, or an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, each of which may have a substituent.
Z is a direct bond or a -CO- group;
^Y3 is preferably a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent), or the like.

The alkenyl group for ^Y1 which may have a substituent includes linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, which may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, and cyclopentadienyl group, but are not limited thereto.

Examples of the alkyl group for ^Y1 which may have a substituent include a linear, branched, monocyclic, or condensed polycyclic alkyl group having 1 to 18 carbon atoms, and a linear, branched, monocyclic, or condensed polycyclic alkyl group having 2 to 18 carbon atoms which is optionally interrupted by one or more -O-. Specific examples of the linear, branched, monocyclic or fused polycyclic alkyl group having 1 to 18 carbon atoms include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isopentyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a bornyl group, and a 4-decylcyclohexyl group. Specific examples of straight-chain and branched-chain alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include, but are not limited to, _-CH2- O- _CH3 , -CH2 _{-CH2 -} O- _CH2 - _CH3 , _{-CH2- CH2} - _CH2 -O- _CH2 - _CH3 , -( _CH2 - _CH2 -O) _n - _CH3 (wherein n is 1 to 8), -( _CH2 - _CH2 - _CH2 -O) _m - _CH3 (wherein m is 1 to 5), _-CH2 -CH( _CH3 )-O- _CH2 - _CH3 , _-CH2 -CH-( _OCH3 ) ₂ and the like.

Specific examples of monocyclic or condensed polycyclic alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include, but are not limited to, the following:

The alkyloxy group for ^Y1 which may have a substituent includes a linear, branched, monocyclic, or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or a linear, branched, monocyclic, or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more -O-. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include, but are not limited to, a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, a dodecyloxy group, an octadecyloxy group, an isopropyloxy group, an isobutyloxy group, an isopentyloxy group, a sec-butyloxy group, a tert-butyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a tert-octyloxy group, a neopentyloxy group, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, an adamantyloxy group, a norbornyloxy group, a boronyloxy group, and a 4-decylcyclohexyloxy group. Specific examples of straight-chain and branched-chain alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include, but are not limited to, -O- _CH2 -O- _CH3 , -O- _CH2 - _CH2 -O- _CH2 - _CH3 , -O- _CH2 - _CH2 - _CH2 -O- _CH2 - _CH3 , -O-( _CH2 - _CH2 -O) _n - _CH3 (wherein n is 1 to 8), -O-( _CH2 - _CH2 - _CH2 -O) _m - _CH3 (wherein m is 1 to 5), -O- _CH2 -CH( _CH3 )-O- _CH2 - _CH3 , -O- _CH2 -CH-( _OCH3 ) ₂ and the like.

Specific examples of monocyclic or condensed polycyclic alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- include, but are not limited to, the following:

The aryl group for ^Y1 which may have a substituent includes a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 9-anthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a 5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a 1-acenaphthyl group, a 2-fluorenyl group, a 9-fluorenyl group, a 3-perylenyl group, an o-tolyl group, Examples of the aryl group include, but are not limited to, aryl, p-tolyl, p-tolyl, 2,3-xylyl, 2,5-xylyl, mesityl, p-cumenyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-chlorophenyl, p-bromophenyl, p-hydroxyphenyl, m-carboxyphenyl, o-mercaptophenyl, p-cyanophenyl, m-nitrophenyl, and m-azidophenyl groups.

The aryloxy group for ^Y1 which may have a substituent includes a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-anthryloxy group, a 9-phenanthryloxy group, a 1-pyrenyloxy group, a 5-naphthacenyloxy group, a 1-indenyloxy group, a 2-azulenyloxy group, a 1-acenaphthyloxy group, and a 9-fluorenyloxy group, but are not limited to these.

The heterocyclic group in ^Y1 which may have a substituent includes an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and examples thereof include a 2-thienyl group, a 2-benzothienyl group, a naphtho[2,3-b]thienyl group, a 3-thianthrenyl group, a 2-thianthrenyl group, a 2-furyl group, a 2-benzofuryl group, a pyranyl group, an isobenzofuranyl group, a chromenyl group, a xanthenyl group, a phenanyl group, noxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, aH-carbazolyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, Examples of the alkyl group include, but are not limited to, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a pyrazolidinyl group, a pyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinyl group, an isoindolinyl group, a quinuclidinyl group, a morpholinyl group, a thioxanthryl group, a 4-quinolinyl group, a 4-isoquinolyl group, a 3-phenothiazinyl group, a 2-phenoxathiinyl group, and a 3-coumarinyl group.

The heterocyclic oxy group for ^Y1 which may have a substituent includes a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom and having 4 to 18 carbon atoms. Specific examples include a 2-furanyloxy group, a 2-thienyloxy group, a 2-indolyloxy group, a 3-indolyloxy group, a 2-benzofuryloxy group, a 2-benzothienyloxy group, a 2-carbazolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group, but are not limited thereto.

The alkylsulfanyl group for ^Y1 which may have a substituent includes linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 20 carbon atoms. Specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a pentylsulfinyl group, a hexylsulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decylsulfinyl group, a dodecylsulfinyl group, an octadecylsulfinyl group, a cyanomethylsulfinyl group, and a methyloxymethylsulfinyl group, but are not limited to these.

The arylsulfanyl group for ^Y1 which may have a substituent includes a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms. Specific examples thereof include, but are not limited to, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthrylthio group.

The arylsulfinyl group which may have a substituent in ^Y1 is preferably an arylsulfinyl group having 6 to 30 carbon atoms. Specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, a 2-methylphenylsulfinyl group, a 2-methyloxyphenylsulfinyl group, a 2-butyloxyphenylsulfinyl group, a 3-chlorophenylsulfinyl group, a 3-trifluoromethylphenylsulfinyl group, a 3-cyanophenylsulfinyl group, a 3-nitrophenylsulfinyl group, a 4-fluorophenylsulfinyl group, a 4-cyanophenylsulfinyl group, a 4-methyloxyphenylsulfinyl group, a 4-methylsulfanylphenylsulfinyl group, a 4-phenylsulfanylphenylsulfinyl group, and a 4-dimethylaminophenylsulfinyl group, but are not limited thereto.

The alkylsulfonyl group for ^Y1 which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, and a methyloxymethylsulfonyl group, but are not limited to these.

The arylsulfonyl group which may have a substituent in Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, a 2-methyloxyphenylsulfonyl group, a 2-butyloxyphenylsulfonyl group, a 3-chlorophenylsulfonyl group, a 3-trifluoromethylphenylsulfonyl group, a 3-cyanophenylsulfonyl group, a 3-nitrophenylsulfonyl group, a 4-fluorophenylsulfonyl group, a 4-cyanophenylsulfonyl group, a 4-methyloxyphenylsulfonyl group, a 4-methylsulfanylphenylsulfonyl group, a 4-phenylsulfanylphenylsulfonyl group, and a 4-dimethylaminophenylsulfonyl group, but are not limited thereto.

The acyl group in ^Y1 which may have a substituent includes a hydrogen atom or a carbonyl group having a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms bonded thereto, a carbonyl group substituted with an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group having a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms bonded thereto, a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, Specific examples include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, a cyclopentylcarbonyl group, a cyclohexylcarbonyl group, an acryloyl group, a methacryloyl group, a crotonoyl group, an isocrotonoyl group, an oleoyl group, and the like. Examples of the alkyl group include, but are not limited to, a cinnamoyl group, a benzoyl group, a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, a butyloxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, a trifluoromethyloxycarbonyl group, a benzoyl group, a toluoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a 9-anthrylcarbonyl group, a phenyloxycarbonyl group, a 4-methylphenyloxycarbonyl group, a 3-nitrophenyloxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 2-methylsulfanylphenyloxycarbonyl group, a 1-naphthoyloxycarbonyl group, a 2-naphthoyloxycarbonyl group, a 9-anthryloxycarbonyl group, a 3-furoyl group, a 2-thenoyl group, a nicotinoyl group, and an isonicotinoyl group.

The acyloxy group for ^Y1 which may have a substituent includes an acyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group.

Examples of the amino group in ^Y1 which may have a substituent include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

Here, examples of alkylamino groups include, but are not limited to, methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino, nonylamino, decylamino, dodecylamino, octadecylamino, isopropylamino, isobutylamino, isopentylamino, sec-butylamino, tert-butylamino, sec-pentylamino, tert-pentylamino, tert-octylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, cyclododecylamino, 1-adamantamino, and 2-adamantamino groups.

Examples of dialkylamino groups include, but are not limited to, dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino, didodecylamino, dioctadecylamino, diisopropylamino, diisobutylamino, diisopentylamino, methylethylamino, methylpropylamino, methylbutylamino, methylisobutylamino, cyclopropylamino, pyrrolidino, piperidino, and piperazino groups.

Examples of arylamino groups include, but are not limited to, anilino groups, 1-naphthylamino groups, 2-naphthylamino groups, o-toluidino groups, m-toluidino groups, p-toluidino groups, 2-biphenylamino groups, 3-biphenylamino groups, 4-biphenylamino groups, 1-fluoreneamino groups, 2-fluoreneamino groups, 2-thiazoleamino groups, and p-terphenylamino groups.

Examples of diarylamino groups include, but are not limited to, diphenylamino groups, ditolylamino groups, N-phenyl-1-naphthylamino groups, and N-phenyl-2-naphthylamino groups.

Examples of alkylarylamino groups include, but are not limited to, N-methylanilino, N-methyl-2-pyridino, N-ethylanilino, N-propylanilino, N-butylanilino, N-isopropyl, N-pentylanilino, N-ethylanilino, and N-methyl-1-naphthylamino groups.

The phosphinoyl group for ^Y1 which may have a substituent includes a phosphinoyl group having 2 to 50 carbon atoms. Specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenylphosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, and a bis(2,4,6-trimethylphenyl)phosphinoyl group, but are not limited thereto.

The carbamoyl group in ^Y1 which may have a substituent includes a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, an N-hexylcarbamoyl group, an N-cyclohexylcarbamoyl group, an N-octylcarbamoyl group, an N-decylcarbamoyl group, an N-octadecylcarbamoyl group, an N-phenylcarbamoyl group, an N-2-methylphenylcarbamoyl group, an N-2-chlorophenylcarbamoyl group, an N-2-isopropoxyphenylcarbamoyl group, an N- Examples of such alkyl groups include, but are not limited to, a (2-ethylhexyl)phenylcarbamoyl group, an N-3-chlorophenylcarbamoyl group, an N-3-nitrophenylcarbamoyl group, an N-3-cyanophenylcarbamoyl group, an N-4-methoxyphenylcarbamoyl group, an N-4-cyanophenylcarbamoyl group, an N-4-methylsulfanylphenylcarbamoyl group, an N-4-phenylsulfanylphenylcarbamoyl group, an N-methyl-N-phenylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-dibutylcarbamoyl group, and an N,N-diphenylcarbamoyl group.

The sulfamoyl group for ^Y1 which may have a substituent includes a sulfamoyl group having 0 to 30 carbon atoms. Specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N,N-dialkylsulfamoyl group, an N,N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chloro ... Examples of the aryl group include, but are not limited to, a nitrophenylsulfamoyl group, an N-3-nitrophenylsulfamoyl group, an N-3-cyanophenylsulfamoyl group, an N-4-methoxyphenylsulfamoyl group, an N-4-cyanophenylsulfamoyl group, an N-4-dimethylaminophenylsulfamoyl group, an N-4-methylsulfanylphenylsulfamoyl group, an N-4-phenylsulfanylphenylsulfamoyl group, an N-methyl-N-phenylsulfamoyl group, an N,N-dimethylsulfamoyl group, an N,N-dibutylsulfamoyl group, and an N,N-diphenylsulfamoyl group.

The alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and ^amino group which may have a substituent in Y2 are synonymous with the alkenyl group which may have a substituent, alkyl group which may have a substituent, alkyloxy group which may have a substituent, aryl group which may have a substituent, aryloxy group which may have a substituent, heterocyclic group which may have a substituent, heterocyclic oxy group which may have a substituent, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, alkylsulfonyl group which may have a substituent, acyloxy group which may have a substituent, and amino group which may have a substituent in R1 described above.

Examples of the substituents in ^Y1 and ^Y2 include halogen groups such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylamino groups such as a methylamino group and a cyclohexylamino group; a dimethylamino group, a diethylamino group, a morpholino group, a piperidino group, Examples of the alkyl group include dialkylamino groups such as dino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, heterocyclic groups such as furyl group, thienyl group, as well as hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfoniumyl group, and triphenylphenacylphosphoniumyl group.
Furthermore, one or more of these substituents may be present, or one or more types of these substituents may be present, and furthermore, the hydrogen atoms of these substituents may be further substituted with other substituents.

Among the oxime ester photopolymerization initiators represented by general formula (5), the oxime ester photopolymerization initiators represented by the following general formula (6) or (7) have excellent sensitivity and are more preferred.

[Oxime ester photopolymerization initiator represented by formula (4)]
General formula (4)

General formula (6) corresponds to the case where ^Y3 in general formula (5) is a Ph-S-Ph- group, and ^Y4 to ^Y6 are preferably a hydrogen atom, an alkyl group or an aryl group which may have a substituent, or an acyl group. The alkyl group which may have a substituent or the aryl group which may have a substituent in ^Y4 to ^Y6 has the same meaning as the alkyl group or aryl group in ^Y1 and ^Y2 .

[Oxime ester photopolymerization initiator represented by formula (5)]
General formula (5)

In general formula (6a), Z in general formula (6) corresponds to a -CO- group. Further, it is more preferable that ^Y1 is an aryl group which may have a substituent, ^Y2 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, ^Y4 and ^Y6 are each a hydrogen atom, and it is even more preferable that ^Y5 is a hydrogen atom or ^a -CO- group.

Examples of ^Y7 include halogen groups such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylamino groups such as a methylamino group and a cyclohexylamino group; Examples of such groups include dialkylamino groups such as diethylamino, diethylamino, morpholino, and piperidino groups, arylamino groups such as phenylamino and p-tolylamino groups, alkyl groups such as methyl, ethyl, tert-butyl, and dodecyl groups, aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, and benzofuranyl groups, and heterocyclic groups such as furyl and thienyl groups, as well as hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, cyano groups, trifluoromethyl groups, trichloromethyl groups, trimethylsilyl groups, phosphinico groups, phosphono groups, trimethylammonium groups, dimethylsulfoniumyl groups, and triphenylphenacylphosphoniumyl groups.

More preferred as the substituent for ^Y2 are cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclooctadecyl groups.

Specific examples of the oxime ester photopolymerization initiator represented by general formula (5a) include photopolymerization initiators represented by the following chemical formula (5a-1) or (5a-2).

[Oxime ester photopolymerization initiator represented by formula (5b)]
General formula (5b)

General formula (5b) corresponds to the case where Z in general formula (5) is a direct bond. In the oxime ester photopolymerization initiator represented by general formula (5b), ^Y1 and ^Y2 are preferably alkyl groups having 1 to 20 carbon atoms which may have a substituent, and at least one of ^Y4 to ^Y6 is preferably an acyl group which may have a substituent. Specifically, the photopolymerization initiator is represented by the following chemical formula (5a-1) or (5a-2), etc.

[Oxime ester photopolymerization initiator represented by formula (6)]
General formula (6)

General formula (6) corresponds to the case where Y ³ in general formula (4) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ have the same meaning as the substituents in Y ¹ and Y ² .

Furthermore, it is preferable that ^Y1 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, ^Y2 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and ^Y7 to ^Y14 are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

When Z in general formula (6) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (6a) is preferred.

"Oxime ester photopolymerization initiator represented by general formula (6a)"
General formula (6a)

General formula (6a) corresponds to the case where Z in general formula (6) is a direct bond, Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁰ and Y ¹² to Y ¹³ in general formula (6) are hydrogen atoms.
Furthermore, Y ¹¹ is preferably a Y ¹⁵ -CO- group or a nitro group. Y ¹⁵ has the same meaning as the substituent in Y ¹ and Y ² , and is preferably an aryl group which may have a substituent. The Y ¹⁵ -CO- group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group which may further have a substituent. More preferably, it is a benzoyl group which may have a substituent, or a nitro group. Y ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

The substituent in the benzoyl group which may have a substituent is preferably an alkyl group or an alkyloxy group having 1 to 20 carbon atoms. Further, as the alkyl group, a methyl group or an ethyl group is preferable, and among the alkyloxy groups, a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more -O- is preferable, which has the same meaning as the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one ^or more -O- in Y1.

^Y2 is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and the substituent is preferably a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclooctadecyl group. Also, an aryl group which may have a substituent is preferably an alkyl group having 1 to 20 carbon atoms which may have a further substituent, or an alkoxy group such as a methoxy group, an ethoxy group, or a tert-butoxy group.

Specific examples of the oxime ester photopolymerization initiator represented by general formula (6a) include photopolymerization initiators represented by the following chemical formulas (6a-1) to (6a-6).

"Oxime ester photopolymerization initiator represented by general formula (6b)"
When Z in formula (6) is a --CO-- group, an oxime ester photopolymerization initiator represented by the following formula (6b) is preferred.

General formula (6b)

General formula (6b) corresponds to the case where Z in general formula (6) is a -CO- group and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, and is an oxime ester photopolymerization initiator having a keto-type carbazole group. ^{Y 7} to Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ is preferably an aryl group which may have a substituent. The substituent of the aryl group which may have a substituent is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, and more preferably a benzoyl group.

Specific examples of the oxime ester photopolymerization initiator represented by general formula (6b) include photopolymerization initiators represented by the following chemical formulas (6b-1) to (6b-4).

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (IRGACURE OXE01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE02) (all manufactured by BASF), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.), etc. In addition, it is also possible to use oxime ester-based photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc.

The content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, based on the total solid content of the photosensitive coloring composition (100 parts by mass), and more preferably 0.5 to 10 parts by mass from the viewpoint of photocurability and developability. If it is less than 0.1 parts by mass, the adhesion of the formed pattern to the substrate will be poor, and if it exceeds 20 parts by mass, problems with developability may occur, and a decrease in brightness may occur during the heat treatment process after pattern formation.

<Polymerization inhibitor>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent photosensitivity due to diffracted light from a mask during exposure. By adding a polymerization inhibitor, it is possible to obtain an effect of preventing curing from progressing beyond the desired pattern due to chain polymerization caused by exposure to light.

Polymerization inhibitors include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of the polymerization inhibitor include alkyl resorcinol compounds such as 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol, alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone, phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine, phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin. The content of the polymerization inhibitor is preferably 0.01 to 1.0 parts by mass relative to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor becomes greater, resulting in improved taper linearity, reduced coating wrinkles, pattern resolution, etc.

<Ultraviolet absorbing agent>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function other than a photopolymerization initiator. The content of the ultraviolet absorber relative to the total solid content in the photosensitive coloring composition is preferably 0.05 to 3.0% by weight. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small, the taper part of the photosensitive coloring composition pattern is elongated, it becomes difficult to form a high-definition fine pixel pattern, and the amount of residue increases. If the content is more than the above, problems such as the generation of insoluble matter and reduced adhesion may occur.

(Absorbance)
The absorbance of the ultraviolet absorbent at a wavelength of 365 nm is preferably 0.4 or more.
The absorbance is a measurement value when the ultraviolet absorber (E) is dissolved in a solvent such as chloroform that has no absorption at a wavelength of 365 nm and diluted to 10 mg/L, and the measurement method is described below. This method utilizes the relationship between solution concentration and light absorption known as the Lambert-Beer law. In other words, when a solution of a certain concentration is sealed in a transparent container with a certain thickness and light with intensity _I0 is irradiated from one side of the container and the light with intensity I emerging from the opposite side is observed, the incident light is absorbed by the solution inside the container and its intensity is weakened. It is known that the weakening of the intensity is proportional to the concentration of the solution. The relational equation that represents this law, where A is the absorbance, is as follows:
A=-Log(I ₀ /I)=abc
Here, a is a proportionality constant, b is the thickness of the solution, and c is the solution concentration.

Further, the ultraviolet absorber is preferably a benzotriazole-based organic compound, a benzophenone-based organic compound, or a triazine-based organic compound. Benzotriazole-based organic compounds having an absorbance of 0.4 or more at a wavelength of 365 nm include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol]. Benzophenone-based organic compounds include 2,2-dihydroxy-4,4-dimethoxybenzophenone. Triazine-based organic compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.
Specific examples include BASF's "TINUVIN P" (absorbance 0.40), "TINUVIN 326" (absorbance 0.48), and "TINUVIN 360" (absorbance 0.40), Shipro Chemical's "Seesorb 107" (absorbance 0.60), and ADEKA's "ADEKA STAB LA-F70" (absorbance 0.90).
<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of the sensitizer include a phthalocyanine derivative, a tetraazaporphyrazine derivative, a tetraquinoxalylporphyrazine derivative, a naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetraphylline derivative, an annulene derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, a metal arene complex, an organic ruthenium complex, or a Michler's ketone derivative, an α-acyloxy ester, an acylphosphine oxide, a methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3', or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone. These sensitizers may be used alone or in combination of two or more at any ratio as required.

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

The content of the sensitizer is preferably 3 to 60 parts by mass relative to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoints of photocurability and developability.

<Antioxidants>
The coloring composition for color filters of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition for color filters from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and can increase the transmittance of the coating film. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound that has an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, etc. can be used.

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

Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butyl Examples of such compounds include 2,2'-thiodiethyl bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide). Other compounds that have a hindered phenol structure, such as oligomers and polymers, can also be used.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 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, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, etc. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

Phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl-4,4'-butylidene bis(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-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-ditert-butyl-6-methylphenyl) phosphite, etc. Other oligomer and polymer type compounds having a phosphite structure can also be used.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol. Other oligomer and polymer type compounds with a thioether structure can also be used.

As benzotriazole-based antioxidants, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

Specific examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 2-hydroxy-4-chlorobenzophenone. Other oligomer and polymer compounds having a benzophenone structure can also be used.

Triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)-1,3,5-triazine. Other oligomer and polymer compounds having a triazine structure can also be used.

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

These antioxidants can be used alone or in a mixture of two or more in any ratio as needed.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on the solid content of the coloring composition for color filters, since this provides good brightness and sensitivity.

<Amine compounds>
The coloring composition of the present invention may contain an amine compound that has the function of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
In order to improve the leveling property of the composition on a transparent substrate, it is preferable to add a leveling agent to the coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total mass of the coloring composition (100% by mass).

Particularly preferred leveling agents are those that have hydrophobic and hydrophilic groups in the molecule, and are characterized by low solubility in water despite having hydrophilic groups, and low surface tension reducing ability when added to a coloring composition. Furthermore, those that have good wettability to glass plates despite their low surface tension reducing ability are useful, and those that can sufficiently suppress electrostatic charging in an amount added that does not cause defects in the coating film due to foaming are preferably used. As a leveling agent having such preferred characteristics, dimethylpolysiloxanes having polyalkylene oxide units can be preferably used. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxanes may have both polyethylene oxide units and polypropylene oxide units.

The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

The leveling agent may contain an anionic, cationic, nonionic or amphoteric surfactant as a supplement. Two or more types of surfactants may be mixed together.
Examples of anionic surfactants that are added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonates, sodium alkyl diphenyl ether disulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, and the like.

Examples of cationic surfactants that can be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that can be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
In addition, the photosensitive coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., as necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and any curing agent may be used as long as it can react with the thermosetting resin. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferably mentioned. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 ... dazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, 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.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting resin.

<Other additives>
The photosensitive coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity over time. Also, an adhesion improver such as a silane coupling agent may be contained to improve adhesion to a transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the colorant.

Adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agents include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition.

<Dispersion Aid>
When dispersing the colorant in the binder resin, a dispersant such as a dye derivative, a resin-type dispersant, a surfactant, etc. may be appropriately contained. Since the dispersant has a large effect of preventing reagglomeration of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the binder resin using the dispersant has good brightness and viscosity stability.

(Dye Derivatives)
The coloring composition for color filters of the present invention can contain, as a dye derivative, a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. As such dye derivatives, for example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, and Japanese Patent No. 4585781 can be used, and these can be used alone or in a mixture of two or more kinds. When a dye derivative is used, it is preferable to use one having a quinophthalone skeleton from the viewpoint of viscosity stability.

Also, dye derivatives having a copper phthalocyanine structure as the base skeleton are preferred because they improve the dispersibility of the colorant and also improve the heat resistance and light resistance of the coloring composition. It is preferred to add 5 to 40 parts by mass of dye derivatives having a copper phthalocyanine structure as the base skeleton per 100 parts by mass of aluminum phthalocyanine pigment in the colorant.

The coloring composition for color filters of the present invention has excellent stability by using both a basic resin-type dispersant with an amine value of 10 to 300 mg KOH/g and a dye derivative having a basic or acidic substituent.

From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 1.0 part by mass or more, more preferably 3 parts by mass or more, and most preferably 5 parts by mass or more, per 100 parts by mass of the colorant. From the viewpoint of heat resistance and light resistance, the content is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less.

(Surfactant)
Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in combination of two or more, but are not necessarily limited to these.

The content of the surfactant is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of adding it, and if the content is more than 55 parts by mass, the excess dispersant may affect the dispersion.

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

<Color filter>
Next, the color filter for a solid-state imaging device of the present invention will be described. The color filter of the present invention has a cyan color filter segment formed using the cyan color photosensitive coloring composition for a color filter for a solid-state imaging device of the present invention. Examples of the color filter include those having a magenta color filter segment and a yellow color filter segment.

The photosensitive coloring composition for solid-state imaging devices of the present invention is used to form a cyan color filter segment, and the filter segments of each color other than the above can be formed using a conventionally used green coloring composition, red coloring composition, or blue coloring composition. The coloring compositions of each color other than the coloring composition of the present invention can be formed using each coloring composition containing each color pigment, the binder resin, the photopolymerizable composition, etc. Furthermore, it can also be used in combination with magenta and yellow file segments other than the above colors.

Pigments forming the magenta filter segment
Examples of magenta pigments for the magenta coloring composition forming the magenta filter segment include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, thioindigo compounds, and perylene compounds. Examples of the magenta pigments classified as C.I. Pigment Red 2, 3, 5, 6, 7, 23, 31, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 123, 130, 144, 146, 149, 150, 166, 168, 169, 177, 179, 178, 181, 184, 185, 190, 194, 202, 206, 209, 220, 221, 224, 238, 254, 255, 269, 282, C.I. Pigment Violet 19, and derivatives thereof are listed. In particular, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 124, C.I. Pigment Red 126, C.I. Pigment Red 128, C.I. Pigment Red 129, C.I. Pigment Red 130, C.I. Pigment Red 131, C.I. Pigment Red 132, C.I. Pigment Red 133, C.I. Pigment Red 134, C.I. Pigment Red 135, C.I. Pigment Red 136, C.I. Pigment Red 137, C.I. Pigment Red 138, C.I. Pigment Red 139 ... Preferred are C.I. Pigment Red 150 and C.I. Pigment Red 282. The magenta pigments can be used alone or in combination of two or more kinds.

<Dye forming yellow filter segment>
The yellow colorant for the yellow coloring composition forming the yellow filter segment may be a yellow pigment or a yellow dye.
As the yellow pigment, organic or inorganic pigments can be used alone or in combination of two or more kinds, and a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, is preferred, and an organic pigment is usually used. As the organic pigment, a commercially available one can be used, and a natural colorant and an inorganic pigment can be used in combination depending on the hue of the desired filter segment.

Specific examples of yellow organic pigments that can be used in the coloring composition are shown below. Yellow pigments include C.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, and quinophthalone pigments described in Japanese Patent No. 4993026 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, the yellow pigment may be C.I. It is preferable that the pigment is at least one selected from the group consisting of Pigment Yellow 138, 139, 150, and 185.

Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, and oxazine dyes.

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

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

Also included are C.I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106, etc.

Also, C.I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191, 192, 194, 195, etc. are also included.

Also included are C.I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184:1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, and 251.

<Color filter segment for solid-state imaging device>
The color filter segments according to the present invention can be formed by any known method without any particular limitations. However, since the filter segments of the imaging element are very fine, ranging from submicrons to several tens of microns, it is preferable to use optical lithography.
An embodiment of the present invention is a method for producing a color filter having a color filter segment obtained by curing the above-mentioned colored composition. The color filter includes a color filter segment obtained by curing the colored composition according to the embodiment of the present invention described above.
The color filter according to this embodiment includes the above-mentioned cyan color filter segment, magenta filter segment, and yellow filter segment. The color filter segments other than those according to the present invention may be formed using a known coloring composition that contains a color pigment, a color dye, or both a color pigment and a color dye. There is no particular restriction on the method for forming the color filter segments, but it is common to use a photosensitive coloring composition that is a negative resist.

When a color filter segment is formed on a corresponding photoelectric conversion element, a negative color resist layer is formed by a negative green film formed from a negative photosensitive green composition, and the thickness of the negative color resist layer in this case is set in the range of 0.1 μm to 3.0 μm.
The surface of the negative color resist layer formed by the negative color film is exposed to pattern light using a photomask at multiple portions corresponding to multiple photoelectric conversion elements to be formed. The photomask has dimensions 4 to 5 times the dimensions of the pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure.
This photomask is a 4-5x reticle, and has a pattern 4-5x larger than the size of the pattern to be exposed on the surface of the negative color resist layer.Then, using a stepper exposure device (not shown), the photomask pattern is reduced to 1/4-1/5 and exposed on the surface of the negative color resist layer.
Following the exposure step, an alkali development treatment (development step) is carried out to dissolve the uncured parts after exposure into a developer, leaving the photocured parts. This development step allows the formation of a patterned coating made of color filter segments.

The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and these may be combined with a swing method, a spin method, an ultrasonic method, etc.
It is also possible to prevent uneven development by pre-wetting the surface to be developed with water or the like before contacting the developing solution. As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying circuitry is preferable. The developing temperature is usually 20°C to 30°C, and the developing time is 20 to 90 seconds.
Examples of the alkaline agent contained in the developer include organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, and potassium hydrogen carbonate. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used. When a developer made of such an alkaline aqueous solution is used, the developer is generally washed (rinsed) with pure water after development to remove excess developer, and then dried.
Finally, the filter segment thus formed is subjected to a hardening treatment.

In the manufacturing method of the present invention, after the above-mentioned colored layer forming step, exposure step, and development step are performed, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually a thermal curing treatment at 100°C to 270°C. When light is used, it can be performed by g-rays, h-rays, i-rays, excimer lasers such as KrF and ArF, electron beams, X-rays, etc., but it is preferable to perform it at a low temperature of about 20 to 50°C using an existing high-pressure mercury lamp, and the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. When post-exposure and post-heating are used in combination, it is preferable to perform post-exposure first.
The colored layer forming step, the exposure step, and the development step (and further, the curing step, if necessary) described above are repeated a number of times corresponding to the desired number of hues, thereby producing color filter segments of the desired hues.

<Solid-state imaging element>
The solid-state imaging element of the present invention includes the color filter segment of the present invention. The configuration of the solid-state imaging element of the present invention is not particularly limited as long as it includes the color filter segment for the solid-state imaging element of the present invention and functions as a solid-state imaging element, and examples of the configuration include the following.
The solid-state imaging element has a substrate on which are disposed a plurality of photodiodes constituting a light receiving area of the solid-state imaging element (such as a CCD sensor, a CMOS sensor, or an organic CMOS sensor) and a transfer electrode made of polysilicon or the like; a light-shielding film made of tungsten or the like with only the light receiving portion of the photodiode being opened is disposed on the photodiodes and the transfer electrode; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode; and a color filter segment for the solid-state imaging element of the present invention is disposed on the device protection film.
Furthermore, the device may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided on the device protection layer and below the color filter segments (on the side closer to the substrate), or the focusing means is provided on the color filter segments.
The organic CMOS sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material is responsible for capturing light and converting it into an electric signal, and the inorganic material is responsible for extracting the electric signal to the outside, and in principle, the aperture ratio for incident light can be made 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for miniaturizing filter segments.
The arrangement of the color filter segments is not particularly limited, and any known method can be used.

The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. Also, "PGMAc" means propylene glycol monomethyl ether acetate.

The methods for measuring the weight average molecular weight (Mw) of the resin, the average molecular weight of the basic resin-type dispersant, and the amine value of the basic resin-type dispersant, as well as the methods for calculating the number of halogen substitutions in the pigment and the halogen distribution width in the pigment, are as follows:

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

(Average molecular weight of basic resin type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the basic resin-type dispersant are polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, a SUPER-AW3000 as a column, and an N,N-dimethylformamide solution of 30 mM triethylamine and 10 mM LiBr as an eluent.

(Amine value of basic resin type dispersant)
The amine value of the basic resin-type dispersant is a value calculated by converting the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 into a solid content value.

(Number of halogen substitutions in pigment)
The number of halogen substitutions in the pigment was obtained by burning the pigment by an oxygen combustion flask method, absorbing the combustion product in water, analyzing the liquid by an ion chromatograph (ICS-2000 ion chromatograph, manufactured by DIONEX Corporation) to quantify the amount of halogen, and converting it into the number of halogen substitutions.

(Halogen distribution range in pigment)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (AutofleXIII (TOF-MS), manufactured by Bruker Daltonics). The halogen content was determined by calculating the signal intensity (each peak value) of the molecular ion peak corresponding to each component in the mass spectrum obtained by mass spectrometry of the pigment powder and the integrated value (total peak value) of each peak value, and then calculating the ratio of each peak value to the total peak value. The halogen distribution width was determined by counting the number of peaks whose ratio of each peak value to the total peak value was 1% or more.

<Method of manufacturing finely processed pigment>
(Micronized Pigment (P-1))
Into a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment represented by formula (50), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20°C for 6 hours. Thereafter, the reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. Into a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added, and the mixture was stirred at 80°C for 1 hour. Thereafter, the mixture was filtered, washed with water, and dried, to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-neck flask, and the mixture was heated to 90° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-1) represented by the following formula (51). The halogen distribution width was 9.

Equation (50)

Equation (51)

(Micronized Pigment (P-2))
Into a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment represented by the above formula (50), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20°C for 4 hours. Thereafter, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. Into a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added, and the mixture was stirred at 80°C for 1 hour. Thereafter, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 8.0 bromine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 15.8 parts of diphenyl phosphate were added to a three-neck flask, and the mixture was heated to 90° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-2) represented by the following formula (52). The halogen distribution width was 9.

Equation (52)

(Micronized Pigment (P-3))
203 parts of aluminum bromide, 47 parts of sodium bromide, and 5 parts of ferric bromide were heated to melt, and 50 parts of the phthalocyanine pigment represented by formula (50) were added at 140°C. The mixture was heated to 160°C, and reacted at 160°C for 7 hours while blowing in 215.4 parts of bromine. The reaction mixture was poured into 2500 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. The residue was washed with 1% aqueous hydrochloric acid, warm water, 1% aqueous sodium hydroxide solution, and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid, and stirred at 50°C for 3 hours. Then, the sulfuric acid solution was poured into 9800 parts of ice water at 3°C, and the precipitated solid was filtered, washed with water, and dried. Next, 500 parts of 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker, and stirred at 80°C for 1 hour. Thereafter, the mixture was filtered, washed with water and dried to obtain a pigment having an average of 15.0 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 15.0 bromine atoms substituted on the phthalocyanine ring, and 10.8 parts of diphenyl phosphate were added to a three-neck flask, and the mixture was heated to 90° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-3) represented by the following formula (53). The halogen distribution width was 4.

Equation (53)

(Micronized Pigment (P-4))
Into a three-neck flask were added 500 parts of N-methylpyrrolidone, 50 parts of the pigment prepared in (P-2) in which an average of 8.0 bromine atoms are substituted on the phthalocyanine ring, and 13.8 parts of diphenylphosphinic acid, and the mixture was heated to 90° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and then dried to obtain a phthalocyanine pigment (P-4) represented by the following formula (54). The halogen distribution width was 9.

Equation (54)

(Micronized Pigment (P-5))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added to the mixture, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Furthermore, 100 parts of chloroaluminum phthalocyanine were slowly added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3°C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of aluminum phthalocyanine pigment (P-11) represented by the following formula (55).

Equation (55)

Next, 250 parts of aluminum chloride, 60 parts of sodium chloride, and 2.25 parts of iodine were added to a three-necked flask and stirred at 150 ° C for 30 minutes. 50 parts of aluminum phthalocyanine pigment represented by formula (55) was added thereto, and stirred at 155 ° C for 30 minutes to dissolve. 58.5 parts of trichloroisocyanuric acid was further added, and stirred at 190 ° C for 5 hours. Then, the above reaction mixture was poured into 5,000 parts of ice water at 3 ° C, and the precipitated solid was filtered and washed with water. 500 parts of 2.5% sodium hydroxide aqueous solution and the filtered residue were added to a beaker, and stirred at 80 ° C for 1 hour. Then, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 8.1 chlorine atoms were substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.1 bromine atoms substituted on the phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-neck flask, and the mixture was heated to 90° C. and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (P-5) represented by the following formula (56). The halogen distribution width was 8.

Equation (56)

(Micronized Pigment (P-6))
In a reaction vessel, 100 parts of the aluminum phthalocyanine pigment represented by formula (55) and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of the aluminum phthalocyanine pigment represented by the following formula (57).

Equation (57)

Next, 100 parts of the aluminum phthalocyanine pigment represented by formula (57), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80°C for a day and night to obtain a finely divided pigment (P-6).

(Micronized Pigment (P-7))
100 parts of phthalocyanine green pigment C.I. Pigment Green 58 (DIC Corporation "FASTGENGREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded product was added to 3000 parts of warm water, heated to 70 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a day and night to obtain 97 parts of finely divided pigment (P-7).

(Micronized Pigment (P-8))
In a 300 mL flask, 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a finely divided pigment (P-8). The obtained finely divided pigment (P-8) was found to have an average of 12.69 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 8.54, and the average number of chlorine atoms was 4.16, making it a halogenated zinc phthalocyanine pigment.

(Micronized Pigment (P-9))
Zinc phthalocyanine was produced using phthalonitrile and zinc chloride as raw materials. A 1-chloronaphthalene solution of this had light absorption at 600 to 700 nm. Halogenation was carried out by mixing 2.9 parts of sulfuryl chloride, 3.5 parts of anhydrous aluminum chloride, 0.43 parts of sodium chloride, and 1.0 part of zinc phthalocyanine at 40°C. The mixture was reacted at 80°C for 15 hours, and then the reaction mixture was poured into water to precipitate a partially chlorinated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80°C, and dried at 90°C to obtain 2.6 parts of purified partially chlorinated zinc phthalocyanine crude pigment.
1.0 part of this partially chlorinated zinc phthalocyanine crude pigment, 7.0 parts of pulverized sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene were charged into a twin-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 100 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine pigment (P-9). The obtained fine pigment (P-9) had an average composition of ZnPcCl ₁₃ H ₃ (Pc: phthalocyanine) and an average chlorine ratio per molecule of 81.3% based on a halogen content analysis using a mass spectrometer (apparatus name: BRUKER REFLEXII, manufactured by Bruker Daltonics, Inc.).

(Micronized Pigment (P-10))
51.2 parts of phthalodinitrile, 30.4 parts of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 200 parts of n-pentanol were charged and heated and stirred under a nitrogen atmosphere. 13.62 parts of zinc chloride was added thereto at 70 to 75° C., and then the mixture was heated at 95 to 100° C. for 5 hours. The precipitate was collected by filtration, washed with an organic solvent, dried, and purified to obtain crude zinc phthalocyanine.

100 parts of the obtained crude zinc phthalocyanine, 1000 parts of ground sodium chloride, and 160 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 8 hours. After kneading, the mixture was taken out into 100 parts of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a finely divided pigment (P-10) represented by the following formula (58).

Equation (58)

(Micronized Pigment (P-12))
100 parts of C.I. Pigment Yellow 139 (PY139) (BASF "Paliotol Yellow D1819"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of finely divided pigment (P-12).

(Micronized Pigment (P-13))
100 parts of C.I. Pigment Yellow 150 (PY150) (BASF "Yellow Pigment E4GNGT"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of finely divided pigment (P-13).

(Micronized Pigment (P-14))
100 parts of C.I. Pigment Yellow 185 (PY185) (BASF "Paliotol Yellow D1155"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80 ° C. This mixture was added to 2000 parts of hot water, heated to 80 ° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of finely divided pigment (P-14).

<Method of producing basic resin-type dispersant>
(Basic resin type dispersant solution 1)
A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 4.0 parts of AIBN (2,2'-azobisisobutyronitrile) and 133 parts of propylene glycol monomethyl ether acetate, followed by 7.8 parts of ethyl acrylate (EA), 39.0 parts of methyl methacrylate (MMA), 31.2 parts of n-butyl methacrylate (nBMA), and 5.0 parts of 2,2,6,6,-tetramethyl-1-piperidinyloxy radical (TEMPO), and substituted with nitrogen for 30 minutes. After that, the temperature of the reaction solution was raised to 80 ° C. with gentle stirring, and this temperature was maintained for 12 hours to carry out living radical polymerization.
Next, 22.0 parts of N,N-dimethylaminoethyl methacrylate (DM) was dissolved in this reaction solution, and the mixture was substituted with nitrogen for 30 minutes, and living radical polymerization was carried out at 80 ° C. for 12 hours. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the previously synthesized dispersant so that the non-volatile content was 50 mass% to prepare a basic resin type dispersant solution 1. As a result of GPC measurement, the Mw of the polymer was 8100. In this way, a basic resin type dispersant solution 1 with an amine value per solid content of 79 mg KOH / g was obtained.

(Basic resin type dispersant solutions 2 to 4)
Basic resin type dispersant solutions 2 to 4 were obtained in the same manner as basic resin type dispersant solution 1, except that the composition was changed as shown in Table 1.

<Production of Resin-Type Dispersant Having Carboxyl Group>
(Carboxyl-containing resin-type dispersant C1)
(Production Example 1)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecane, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and the mixture was replaced with nitrogen gas, and then heated and stirred at 120°C for 4 hours. After confirming that 98% had reacted by measuring the solid content, 73.3 parts of pyromellitic anhydride were added and reacted at 120°C for 2 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The obtained dispersant was a white solid at room temperature, and the acid value was 49 mgKOH/g. A dispersant (C1) solution with a solid content of 50% was obtained by adjusting the solid content.

(Carboxyl-containing resin-type dispersant C2)
(Production Example 2)
A reaction vessel equipped with a gas inlet tube, a thermostat, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, 40 parts of t-butyl methacrylate, 20 parts of n-butyl acrylate, 20 parts of t-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate, and the inside atmosphere was replaced with nitrogen gas.
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 a solution of 0.1 parts of 2,2′-azobisisobutyronitrile in 90 parts of propylene glycol monomethyl ether acetate was added thereto while reacting for 7 hours. It was confirmed by measuring the solid content that 95% had reacted.
35 parts of trimellitic 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 the mixture was reacted for 7 hours at 100° C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the mixture to a solid content of 50% by measuring the solid content, to obtain a resin-type dispersant (C2) having an acid value of 40 mgKOH/g and a weight average molecular weight of 9000.

(Carboxyl-containing resin-type dispersants C3 to C6)
(Production Examples 3 to 7)
Synthesis was carried out in the same manner as in Production Example 2, except that the raw materials and the amounts charged were used as shown in Table 1, to obtain resin-type dispersants (C3 to C6).

<Method of producing binder resin>
(Preparation of Binder Resin Solution 1)
(Step 1: Polymerization of the resin backbone)
A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, was charged with 100 parts of propylene glycol monomethyl ether acetate (PGMAC), and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction.

(Step 2: Reaction to epoxy groups)
Next, the atmosphere in the flask was replaced with air, and 29 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the reaction was carried out at 120°C for 5 hours, yielding a resin solution with a weight average molecular weight (Mw) of about 10500. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure.

(Step 3: Reaction with hydroxyl groups)
Further, 46 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride is cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal.

(Step 4: Adjustment of non-volatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20% by weight, to obtain a binder resin solution 1. The weight average molecular weight (Mw) was 11,500, and the acid value was 103 mgKOH/g.

(Preparation of Binder Resin Solution 2)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 480.0 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 19.0 parts of meparacumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 28.0 parts of methacrylic acid, 22.4 parts of methyl methacrylate, 11.5 parts of glycerol monomethacrylate, 29.0 parts of benzyl methacrylate, 16.0 parts of n-butyl methacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 12.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.1 parts of dibutyltin laurate, and 26.0 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20 mass%, and a binder resin solution 2 having an acid value of 131 mg KOH / g was obtained.

(Preparation of Binder Resin Solution 3)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 700.0 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 50.0 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 50.0 parts of methacrylic acid, 40 parts of methyl methacrylate, 55.2 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected into the entire amount of the obtained copolymer solution for 1 hour while stirring, and then the solution was cooled to room temperature, and then a mixture of 59.9 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution.
After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content became 20 mass%, and a binder resin solution 3 having an acid value of 104 mgKOH/g was obtained.

(Preparation of Binder Resin Solution 4)
A separable 4-neck flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, and 207 parts of cyclohexanone was charged in the reaction vessel. The temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 37.5 parts of methacrylic acid, 27.5 parts of methyl methacrylate, 5.0 parts of n-butyl methacrylate, 18.7 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained copolymer solution, and then the mixture was cooled to room temperature, and a mixture of 16.3 parts of 2-methacryloyloxyethyl isocyanate (Showa Denko KARENZ MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass, and a binder resin solution 4 with an acid value of 233 mgKOH/g was obtained.

(Preparation of Binder Resin Solution 5)
145 g of propylene glycol monomethyl ether acetate (PGMAC) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred and heated to 120 ° C. while being replaced with nitrogen. Next, 10.1 g (6.0 parts) of azobisisobutyronitrile was added to a monomer mixture consisting of 20.0 g (0.1 mol) of a monomethacrylate having a dicyclopentadiene skeleton (FA-512M manufactured by Hitachi Chemical Co., Ltd.), 108.0 g (1.5 mol) of methacrylic acid, and 31.0 g (0.2 mol) of benzyl methacrylate, relative to 100 parts of the monomer mixture. This was dropped into the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 120 ° C. for 2 hours to perform aging. Next, the atmosphere in the flask was replaced with air, and 122.3 g of glycidyl methacrylate (0.9 mol, 60 mol% of methacrylic acid), 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the aged solution, and the reaction was continued at 120°C for 6 hours. When the solid content acid value reached 1.0, the reaction was terminated, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20% by weight, to obtain a binder resin solution 5. The weight average molecular weight (Mw) was 18,100, and the acid value was 117 mgKOH/g.

(Preparation of Binder Resin Solution 6)
Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 333 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100° C., and then a solution obtained by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 164 g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask over 2 hours, and stirring was continued for a further 5 hours at 100° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% relative to the glycidyl group of the glycidyl methacrylate used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110 ° C., and the reaction was terminated when the solid acid value became 1 mg KOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution. About 2 g of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether acetate was added to the photosensitive transparent resin solution synthesized earlier so that the nonvolatile content was 20 mass% to prepare a photosensitive resin solution, and a binder resin solution 6 with an acid value of 80 mg KOH / g was obtained.

(Preparation of Binder Resin Solution 7)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 196 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80 ° C. and substituted with nitrogen in the reaction vessel. From the dropping tube, 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. PGMAC was added to the resin solution previously synthesized so that the non-volatile content became 20 mass%, and binder resin solution 7 having an acid value of 94 mgKOH/g was obtained.

(Preparation of Binder Resin Solution 8)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 560.0 parts of cyclohexanone was charged in the reaction vessel, which was heated to 80 ° C. and substituted with nitrogen in the reaction vessel. From the dropping tube, 26.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate, 23.0 parts of paracumylphenol ethylene oxide modified acrylate (manufactured by Toa Gosei Co., Ltd., "Aronix M110") 22.0 parts, 31.9 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 52.2 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass%, and a binder resin solution 8 with an acid value of 95 mg KOH / g was obtained.

(Preparation of Binder Resin Solution 9)
A separable 4-neck flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, and 520.0 parts of cyclohexanone was charged in the reaction vessel, which was heated to 80 ° C. and replaced with nitrogen in the reaction vessel. From the dropping tube, a mixture of 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 54.3 parts of 2-hydroxyethyl methacrylate, 66.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour with respect to the total amount of the obtained copolymer solution, and then the mixture was cooled to room temperature, and then a mixture of 64.8 parts of 2-methacryloyloxyethyl isocyanate (Showa Denko KARENZ MOI), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass, and a binder resin solution 9 with an acid value of 23 mgKOH/g was obtained.

<Production of Pigment Dispersion>
[Example 1]
(Preparation of Pigment Dispersion (D-1))
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 5 hours in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to obtain a pigment dispersion (D-1).
The pigment dispersion was adjusted with PGMAc (propylene glycol monomethyl ether acetate) so that the solid content was 20% by mass.
Fine pigment (P-1): 8.4 parts Fine pigment (P-7): 3.6 parts Basic resin type dispersant solution 1: 2.4 parts Resin type dispersant solution C1 having a carboxyl group: 3.6 parts Binder resin solution 1: 25.0 parts Propylene glycol monomethyl ether acetate: 57.0 parts

[Examples 2 to 27, Comparative Examples 1 to 4, 9 to 11]
(Preparation of pigment dispersions (D-2 to 27), (D-29 to 32, 37 to 39))
Pigment dispersions (D-2 to 27), (D-29 to 32, 37 to 39) were obtained in the same manner as for pigment dispersion (D-1), except that the composition was changed as shown in Table 2.

[Example 28]
(Preparation of Pigment Dispersion (D-28))
The following mixture was stirred and mixed to be homogeneous, and then filtered through a 5.0 μm filter to obtain a pigment dispersion (D-28).
Pigment dispersion (D-31): 30.0 parts Pigment dispersion (D-32): 70.0 parts

[Comparative Example 5]
(Preparation of Pigment Dispersion (D-33))
The mixture below was stirred and mixed to be homogenous, and then dispersed for 5 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to obtain a pigment dispersion (D-33).
The pigment dispersion was adjusted with PGMAc (propylene glycol monomethyl ether acetate) so that the solid content was 20% by mass.
Fine pigment (P-6): 10.9 parts Dye derivative (A-1): 1.1 parts Basic dispersant solution 1: 2.4 parts Resin-type dispersant solution C1 having a carboxyl group: 3.6 parts Binder resin solution 1: 25.0 parts Propylene glycol monomethyl ether acetate: 57.0 parts

[Comparative Examples 6 to 8]
(Preparation of Pigment Dispersions (D-34 to 36))
Pigment dispersions (D-34 to 36) were obtained in the same manner as for pigment dispersion (D-33), except that the composition was changed as shown in Table 3.

(Dye Derivatives (A-1 to A-4))
The structures of the dye derivatives (A-1 to A-4) shown in Table 2 are shown below.

(A-1)

(A-2)

(A-3)

(A-4)

<Evaluation of Pigment Dispersion>
The obtained pigment dispersions (D-1 to 39) were evaluated for viscosity stability and light transmittance by the following methods. In the light transmittance evaluation, the pigment dispersions (D-1 to 39) were formed into a coating film substrate with a film thickness of 0.5 μm using a spin coater, and then the evaluation was performed. The evaluation results are shown in Table 4.

(Evaluation of Viscosity Stability of Pigment Dispersion)
The initial viscosity of the resulting pigment dispersions (D-1 to 39) immediately after dispersion and the viscosity over time after accelerated aging at 40° C. for 1 week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25° C. and a rotation speed of 50 rpm. From the initial viscosity and aging viscosity values, the rate of viscosity change over time was calculated using the following formula, and the viscosity stability was evaluated on a two-level scale.
[Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity] | x 100
◎: Rate of change less than 2% ◯: Rate of change 2% or more but less than 5% △: Rate of change 5% or more but less than 10% ×: Rate of change 10% or more

(Measurement of Average Light Transmittance of Dispersion)
The light transmittance of the obtained coated substrate at wavelengths of 300 to 900 nm was measured using a spectrophotometer (Hitachi High-Tech Science Corporation, "U-3310"), and the average light transmittance in the wavelength region described below was evaluated.
(Average transmittance evaluation for wavelength range 400-460 nm)
◯: 75% or more △: 70% or more but less than 75% ×: Less than 70%
(Average transmittance evaluation for wavelength range 480-550 nm)
〇: 90% or more △: 80% or more but less than 90% ×: Less than 80%
(Average transmittance evaluation for wavelength range 620-680 nm)
〇: Less than 10% △: 10% to 20% ×: More than 20%

As shown in Examples 1 to 27, each pigment dispersion had good spectral characteristics as a cyan color and also had good viscosity stability.
Furthermore, when Example 6, which used a codispersion, was compared with Example 28, which used a monodispersed mixture, it was shown that Example 6, which used a codispersion, was superior, particularly in terms of viscosity stability.
In Comparative Examples 1, 2, and 4, the average transmittance was good, but the viscosity stability was very poor. In the other Comparative Examples, the average transmittance in the wavelength region of 400 to 460 nm was very poor, and the spectral characteristics of cyan color were poor.

<Production of Photosensitive Coloring Composition>
[Example 29]
(Preparation of Photosensitive Coloring Composition (R-1))
The mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive green colored composition (R-1).
Pigment dispersion (D-1): 50.9 parts Binder resin solution 1: 6.4 parts Polymerizable compound (Toagosei Co., Ltd. "Aronix M-402"): 4.7 parts Photopolymerization initiator (chemical formula (6b-2)): 0.25 parts Ultraviolet absorber (TINUVIN 326): 0.1 parts Polymerization inhibitor (methylhydroquinone): 0.05 parts Propylene glycol monomethyl ether acetate: 37.6 parts

[Examples 30 to 73, Comparative Examples 12 to 22]
(Preparation of photosensitive coloring compositions (R-2 to R-56))
Photosensitive coloring compositions (R-2 to 56) were obtained in the same manner as the photosensitive coloring composition (R-1), except that the pigment dispersion (D-1) was changed to the pigment dispersion shown in Table 5. In addition, in this specification, Examples 1 to 28, 29 to 33, 37 to 41, and 57 to 73 are reference examples.

The raw materials listed in Table 5 are as follows.
<Polymerizable Compound>
Urethane acrylate: Dipentaerythritol pentaacrylate hexamethylene diisocyanate (reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate)
Aronix M-402 (dipentaerythritol penta- and hexaacrylate) manufactured by Toagosei Co., Ltd.
- Aronix M-350 (trimethylolpropane EO modified triacrylate) manufactured by Toagosei Co., Ltd.

<Ultraviolet absorbing agent>
BASF TINUVIN 326 (benzotriazole compound): 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (absorbance 0.5)

<Evaluation of Photosensitive Coloring Composition>
The light transmittance and viscosity stability of the obtained photosensitive coloring compositions (R-1 to 56) were evaluated by the following methods. The evaluation results are shown in Table 6.

(Measurement of Average Light Transmittance of Photosensitive Composition)
The light transmittance of the obtained coated substrate at wavelengths of 300 to 900 nm was measured using a spectrophotometer (Hitachi High-Tech Science Corporation, "U-3310"), and the average light transmittance in the wavelength region described below was evaluated.
(Average transmittance evaluation for wavelength range 400-460 nm)
◯: 75% or more △: 70% or more but less than 75% ×: Less than 70%
(Average transmittance evaluation for wavelength range 480-550 nm)
〇: 90% or more △: 80% or more but less than 90% ×: Less than 80%
(Average transmittance evaluation for wavelength range 620-680 nm)
〇: Less than 10% △: 10% to 20% ×: More than 20%

(Evaluation of Viscosity Stability of Photosensitive Coloring Composition)
The viscosity stability was measured in the same manner as in the evaluation of the pigment dispersion, and was evaluated according to the following criteria.
[Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity] | x 100
◎: Rate of change less than 2% ◯: Rate of change 2% or more but less than 5% △: Rate of change 5% or more but less than 10% ×: Rate of change 10% or more

The photosensitive coloring composition also showed the same results as the pigment dispersion. As shown in Examples 18 to 34, each photosensitive coloring composition showed good color characteristics as cyan color, and also had good viscosity stability.
Comparing Example 34, which used a co-dispersion, with Example 56, which used a monodispersed mixture, it was shown that Example 34, which used a co-dispersion, was superior in terms of viscosity stability, similar to the evaluation results of the pigment dispersion.
Comparative Examples 12, 13, and 21 had good average transmittance but very poor viscosity stability. Other comparative examples had very poor average transmittance in the wavelength range of 400 to 460 nm, and poor spectral characteristics for cyan color.

<Production of Color Filters>
Next, a photosensitive red coloring composition prepared in the same manner as in Example 18 was applied to a silicon wafer substrate using a spin coater, except that the colorant used in the photosensitive coloring composition (R-1) was replaced with C.I. Pigment Red 122 = 12.0 parts, to form a colored coating. Next, the coating was irradiated with 3000 J / m ² ultraviolet light using an ultra-high pressure mercury lamp through a photomask. Then, the unexposed portion was removed by spray development using an alkaline developer consisting of a 0.05 mass% tetramethylammonium hydroxide aqueous solution, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 5 minutes to form a magenta color filter segment.

Similarly, a photosensitive yellow coloring composition prepared in the same manner as in Example 18 was applied to a silicon wafer substrate using a spin coater, except that the colorant used in the photosensitive coloring composition (R-1) was replaced with P-14 = 12.0 parts, to form a colored coating. Next, the coating was irradiated with 3000 J / m ² ultraviolet light using an ultra-high pressure mercury lamp through a photomask. Then, the unexposed portion was removed by spray development using an alkaline developer consisting of a 0.05 mass% tetramethylammonium hydroxide aqueous solution, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 5 minutes to form a yellow color filter segment to obtain a color filter.

By using the cyan photosensitive coloring composition for color filters for solid-state imaging devices of the present invention, it was possible to prepare a color filter having good viscosity stability and excellent color characteristics as a cyan color.
Therefore, by using a solid-state imaging element equipped with this color filter in mobile phone cameras, in-vehicle sensors, surveillance cameras, and other devices, it will be possible to create devices with significantly improved long-distance shooting capabilities and image resolution.

Claims (7)

A cyan photosensitive coloring composition for a color filter for a solid-state imaging device, comprising a colorant, a resin-type dispersant, a binder resin, a polymerizable compound, a photopolymerization initiator, and an organic solvent,
the resin-type dispersant includes a basic resin-type dispersant having an amine value of 10 to 300 mgKOH/g and a resin-type dispersant having a carboxyl group;
the binder resin is an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain,
A cyan photosensitive coloring composition for a color filter for a solid-state imaging device, comprising a colorant containing a phthalocyanine pigment represented by the following formula (57) and a zinc phthalocyanine compound, and containing 70 parts by mass or more of the phthalocyanine pigment represented by the following formula (57) per 100 parts by mass of the colorant:
Equation (57)
The cyan photosensitive coloring composition for color filters for solid-state imaging devices according to claim 1, characterized in that the zinc phthalocyanine compound contains a halogenated zinc phthalocyanine pigment. The cyan photosensitive coloring composition for color filters for solid-state imaging devices according to claim 1 or 2, characterized in that the cyan coloring composition for color filters for solid-state imaging devices contains a co-dispersion of a phthalocyanine pigment represented by formula (57) and a zinc phthalocyanine compound. The cyan photosensitive coloring composition for color filters for solid-state imaging devices according to any one of claims 1 to 3, wherein when a coating film formed from the cyan photosensitive coloring composition for color filters for solid-state imaging devices has a thickness of 0.5 μm, the coating film has a light transmittance of 70% or more at wavelengths of 400 to 460 nm, an average light transmittance of 80% or more at wavelengths of 480 to 550 nm, and an average light transmittance of 20% or less at wavelengths of 620 to 680 nm. A filter segment formed from the cyan photosensitive coloring composition for a color filter for a solid-state imaging device according to any one of claims 1 to 4. A color filter for a solid-state imaging device, comprising the filter segment according to claim 5 on a substrate. A solid-state imaging device comprising the color filter for solid-state imaging devices according to claim 6.