JP2022113705A - Photosensitive coloring composition of color filter for solid-state imaging elements, color filter, and solid-state imaging element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition used in a color filter for solid-state imaging elements, which has excellent heat resistance and is free of foreign matter, and which is suitable for CF pixel formation by photolithography, and a color filter and a solid-state imaging element using this coloring composition.

SOLUTION: Provided is a photosensitive coloring composition used in a color filter for solid-state imaging elements, said composition including a colorant (A), a binder resin (B), a photoinitiator (C), and a photopolymerizable monomer (D), the colorant (A) containing a diketopyrrolopyrrole pigment (A1) expressed by chemical formula (1) and one or more organic pigments (A2), with the pigment (A1) accounting for 20 mass% to 95 mass% with respect to the total amount of the colorant (A), and the photopolymerizable monomer (D) including an oxime ester initiator.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a photosensitive coloring composition for color filters used in the manufacture of color filters used in color image pickup tube elements, a color filter comprising filter segments formed using the same, and a solid using the same. It relates to an image sensor.

Generally, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is further formed thereon. there is In order to obtain sufficient performance of these transparent electrodes and alignment films, high temperature treatment at 200° C. or higher, preferably 230° C. or higher is generally required in the manufacturing process of forming the color filter. For this reason, at present, a method called a pigment dispersion method, in which a pigment having excellent light resistance and heat resistance is used as a colorant, is mainly used for color filters.

However, a color filter in which pigments are dispersed generally has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to scattering of light by the pigments. That is, light leaks when light should be blocked (OFF state), and transmitted light is attenuated when light should be transmitted (ON state). There is a problem that the upper luminance ratio (contrast ratio) is low.

Therefore, in recent years, in order to realize high luminance and high contrast of color filters, the pigments contained in the filter segments are often used after being subjected to fine processing. However, simply a pigment (a mixture of primary particles and agglomerated secondary particles of primary particles and aggregated secondary particles of what is called crude produced by a chemical reaction and has a particle size of 10 to 100 μm by a pigmentation treatment) can be used in various ways. Even if the pigment is made finer by the finer fine processing method, the pigment whose primary particles or secondary particles have been made finer generally tends to agglomerate. put away. Furthermore, even if the finely divided pigment is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are brought closer to the primary particles as much as possible to stabilize them, a stable coloring composition can be obtained. is very difficult.

Therefore, for example, a pigment composition containing a pigment composed of fine particles often exhibits high viscosity, and not only is it difficult to take out the product from a disperser and transport it, but in the worst case, gelation may occur during storage. It can even make it difficult to use. Therefore, a structure-controlled one having a block type structure (Patent Document 1) or a comb structure (Patent Document 2), a resin type dispersant such as a polyester dispersant having a specific structure (Patent Document 3), etc. are used to improve dispersibility. , a coloring composition having excellent storage stability and a high contrast ratio has been studied. However, even the use of these resin-type dispersants is not sufficient to improve the durability of pigments with increased surface area due to the progress in the miniaturization of pigments. At present, there are problems such as a decrease in heat resistance and poor leveling, and insufficient heat resistance, light resistance, solvent resistance, and the like.

In the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, pigments such as diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, perylene-based pigments, and disazo-based pigments are used as colorants. It is common to use them alone or in combination.

Patent Document 4 discloses a brominated diketopyrrolopyrrole pigment with high contrast,
Furthermore, a technique is disclosed in which the effect can be further enhanced by using a specific dye in combination.

C-MOS (Complementary Metal Oxide Semiconductor
A solid-state imaging device such as a complementary metal oxide semiconductor) and a CCD (Charge Coupled Device) has an additive mixture of B (blue), G (green), and R (red) on its light receiving element. It is common to provide color filters each having a primary color filter segment for color separation. In recent years, as the pixel size has decreased in this solid-state imaging device, the performance requirements for color separation have become more stringent. performance, such as elimination of overlap regions where colors overlap between organic pixels, and the like.

Specifically, in a color filter for a solid-state imaging device, for thinning the organic pattern, for example, the thickness is 1 μm or less, and for the pixel pattern size, it is microscopic, such as 2 μm or less (for example, 0.5 to 2.0 μm). There is a tendency toward size reduction. Due to this tendency, there is a problem that the foreign matter in the color filter and the crystal foreign matter caused by insufficient heat resistance adversely affect the characteristics of the solid-state imaging device.

JP-A-2002-31713 JP-A-11-1515 WO2008/007776 JP 2013-14750 A

An object of the present invention is to provide a photosensitive coloring composition for use in a color filter for a solid-state imaging device, which has good heat resistance, contains little foreign matter, and is suitable for forming CF pixels by photolithography, and a color filter and a solid-state imaging device using the composition. is to provide

That is, the present invention relates to the following [1] to [5].

[1] including a coloring agent (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable monomer (D),
The coloring agent (A) contains a diketopyrrolopyrrole pigment (A1) represented by the following chemical formula (1) and one or more organic pigments (A2),
The pigment (A1) is 20% by mass to 95% by mass with respect to the total amount of the colorant (A),
A photosensitive coloring composition for use in color filters for solid-state imaging devices, wherein the photopolymerizable monomer (D) contains an oxime ester initiator.

[2] The organic pigment (A2) is C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185 and one or more selected from the group consisting of a yellow pigment represented by the following general formula (3), the photosensitive coloring composition for use in a color filter for a solid-state imaging device as described above.

General formula (3)

[In general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or a substituent an aryl group, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups which may have substituents, or substituents of these acidic groups; represents a sulfamoyl group which may have,
Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may combine to form an aromatic ring which may have a substituent. ]

[3] A photosensitive coloring composition for use in a color filter for a solid-state imaging device according to any one of the above, further comprising a pigment derivative.

[4] A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition used in any one of the color filters for solid-state imaging devices described above.

[5] A solid-state imaging device comprising the above color filter.

According to the present invention, there is no pattern missing due to peeling development of the formed pixels, a vertical cross-sectional shape can be maintained, excellent adhesion, and a photosensitive coloring composition used for a color filter for a solid-state imaging device with little residue, A color filter and a solid-state imaging device using it can be provided.

The present invention will be described in detail below.
In this specification, when expressed as "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", Unless otherwise stated, "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide"".
Moreover, "C.I." mentioned in this specification means a color index (C.I.).

<Colorant (A)>
The coloring agent (A) constituting the photosensitive coloring composition (hereinafter sometimes simply referred to as "photosensitive coloring composition") used in the color filter for a solid-state imaging device of the present invention has the following chemical formula (1 ), and one or more pigments selected from the group consisting of diketopyrrolopyrrole pigments represented by the following general formula (2) (A1), and one or more It contains an organic pigment (A2) and/or a dye (a), and the pigment (A1) is 20% by mass to 95% by mass with respect to the total amount of the colorant (A).

It is preferable that the content of the pigment (A1) is within the range of 20% by mass to 95% by mass with respect to the total amount of the colorant (A) because less foreign matter is generated when a color filter for a solid-state imaging device is produced.

[In formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a substituted a phenyl group optionally having a group, —CF ₃ , —OR ¹ , —SR ² , —N(R ³ )R ⁴ , —COOR ⁵ , —CONH ₂ , —CONHR ⁶ , —CON(R ⁷ )R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N(R ¹⁰ )R ¹¹ , wherein R ¹ to R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms; It is an optionally substituted phenyl group or an optionally substituted aralkyl group. However, A and B cannot be hydrogen atoms at the same time. ]

The alkyl group having 1 to 12 carbon atoms may be linear or branched, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, and pentyl. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and the like, but are not limited thereto. do not have.

Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl group having 1 to 4 carbon atoms. phenyl groups having substituents such as groups. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl Examples include, but are not limited to, phenyl groups and the like.

Examples of the aralkyl group which may have a substituent are specifically a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4- Examples include, but are not limited to, a dichlorobenzyl group.

In this specification, the diketopyrrolopyrrole-based pigment represented by the general formula (2) is represented by the following chemical formula (2-1), the following chemical formula (2-2), the following general formula (2-3), and the following general It is preferably one or more pigments selected from the group consisting of formula (2-4). This further improves brightness, contrast, and the effect of suppressing crystal precipitation. Further, R ¹² to R ¹⁴ in the formulas (2-3) and (2-4) are alkyl groups having 4 or more carbon atoms or phenyl groups which may have substituents, and have contrast and crystal precipitation suppressing effects. It is preferable from the point of The reason why these are effective in increasing the contrast and suppressing crystal precipitation is that the steric hindrance effect of bulky substituents such as carboamide groups, phenyl groups, and t-butyl groups having alkyl groups of 4 or more carbon atoms It is thought that this is because the aggregation of is suppressed. In addition, the specific heterodiketopyrrolopyrrole pigment having a carboxamide group, a phenyl group, and a t-butyl group has excellent color characteristics, and does not impair the excellent brightness of the brominated diketopyrrolopyrrole pigment.

[In formulas (2-3) and (2-4),
R ¹² to R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent. ]

Specific examples of the specific heterodiketopyrrolopyrrole pigment of formula (2) that can be used in the present invention are shown below, but are not limited thereto.

The diketopyrrolopyrrole-based pigment used in the present invention is a pigment other than the diketopyrrolopyrrole pigment of formula (1) and the specific heterodiketopyrrolopyrrole pigment of formula (2), as long as the effects of the present invention are not impaired. A diketopyrrolopyrrole pigment may be used in combination. Specifically, C.I. I. Pigment Red 254, 255, 264, 272, C.I. I. Diketopyrrolopyrrole pigments such as Pigment Orange 71, 73, or 81 may include, but are not limited to. Diketopyrrolopyrrole pigments that can be used in combination include C.I. I. Pigment Red 254 is preferred. C. I. Pigment Red 254 is preferable because it is always contained when the specific heterodiketopyrrolopyrrole pigment of formula (2) is produced by a succinic acid diester synthesis method, and the diketopyrrolopyrrole pigment of formula (1) This is because it is less likely to adversely affect the excellent brightness of the pigment.

(Method for producing diketopyrrolopyrrole pigment)
The diketopyrrolopyrrole pigment represented by formula (1) can be produced by a succinic acid diester synthesis method. That is, 2 mol of 4-bromobenzonitrile is added to 1 mol of succinic acid diester in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or alkali metal alkoxide at a high temperature of 80 to 110 ° C. A condensation reaction is performed to produce an alkali metal salt of the diketopyrrolopyrrole compound, and then the alkali metal salt of the diketopyrrolopyrrole compound is protonated using water, alcohol, acid, or the like, A brominated diketopyrrolopyrrole pigment can be obtained. At this time, the primary particle size obtained can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid. The method for producing the diketopyrrolopyrrole pigment represented by formula (1) is not limited to this method.

Specific heterodiketopyrrolopyrrole pigments of formula (2) are described, for example, in the literature Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565.

Further, the specific heterodiketopyrrolopyrrole pigment of formula (2) is C.I. I. It can also be synthesized as a mixture with Pigment Red 254. This is possible by using a method using at least two structurally different benzonitrile compounds in the succinic acid diester synthesis method (hereinafter referred to as "succinic acid diester co-synthesis method"). Specifically, in the method described in Patent Document 5, the plurality of benzonitrile compounds used are 4-
By selecting from chlorobenzonitrile and a benzonitrile compound represented by the following formula (3), the specific heterodiketopyrrolopyrrole pigment of formula (2) can be obtained from C.I. I. It can be produced as a mixture with Pigment Red 254.

C.I. I. When producing a pigment composition containing Pigment Red 254 and a specific heterodiketopyrrolopyrrole pigment, mixture 2 of 4-chlorobenzonitrile and a benzonitrile compound of formula (3) per 1 mol of succinic acid diester react moles. At this time, C.I. I. The mixing ratio (molar ratio) of 4-chlorobenzonitrile and the benzonitrile compound of formula (3) is adjusted so that the mass ratio of Pigment Red 254 and the specific heterodiketopyrrolopyrrole pigment is 97:3 to 85:15. need to adjust. Since reactivity differs depending on the type of benzonitrile compound of formula (3), the mixing ratio (molar ratio) of 4-chlorobenzonitrile and formula (3) varies. In order to keep the mass ratio of the diketopyrrolopyrrole-based pigment composition within the desired range, the mixing ratio (molar ratio) of 4-chlorobenzonitrile and formula (3) is approximately in the range of 80:20 to 98:2. become. Further, in the succinic acid diester co-synthesis method, a diketopyrrolopyrrole pigment (i.e., a diketopyrrolopyrrole pigment containing no chlorine atoms) obtained by reacting 2 mol of the benzonitrile compound of formula (3) with 1 mol of the succinic acid diester. may be generated, but with the mixing ratio in this range, the amount is so small that it has almost no adverse effect.

[In the formula (3), A and B are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, - _CF3 ,
—OR ¹ , —SR ² , —N(R ³ )R ⁴ , —COOR ⁵ , —CONH ₂ , —CONHR ⁶ , —C
ON(R ⁷ )R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N(R ¹⁰ )R ¹¹ , wherein each of R ¹ to R ¹¹ independently has 1 carbon atom; 1 to 12 alkyl groups, optionally substituted phenyl groups, or optionally substituted aralkyl groups.
However, A and B cannot be hydrogen atoms at the same time. ]

The diketopyrrolopyrrole pigment of the present invention can be used by mixing the diketopyrrolopyrrole pigment represented by formula (1) and the specific heterodiketopyrrolopyrrole pigment which are separately produced. Further, a specific heterodiketopyrrolopyrrole pigment synthesized by a succinic acid diester cosynthesis method and C.I. I. A mixture of Pigment Red 254 can also be used by further mixing with a diketopyrrolopyrrole pigment represented by formula (1). In these cases, the pigment may be simply mixed before dispersing, or may be pulverized and mixed by salt milling.

In the diketopyrrolopyrrole pigment of the present invention, the diketopyrrolopyrrole pigment represented by formula (1), the specific heterodiketopyrrolopyrrole pigment of formula (2), and C.I. I. The mass ratio of Pigment Red 254 can be analyzed using TOF-MASS, FD-MASS, LC-MASS or NMR. Alternatively, as disclosed in JP-A-08-199085, a composition having a diketopyrrolopyrrole pigment is stirred with di-tert-butyl dicarbonate and 4-dimethylaminopyridine in tetrahydrofuran at room temperature. Analysis using NMR, MASS, LC-MASS, or the like may be performed after conversion to a soluble diketopyrrolopyrrole compound obtained by. Alternatively, the hydrogen of the NH group of the pyrrolopyrrole ring may be substituted with an alkyl group using an alkyl halide or the like, converted to a soluble diketopyrrolopyrrole, and then subjected to the above analysis.

<Resin Dispersant>
The resin-type dispersant preferably used in the present invention is a resin-type dispersant having a polar site (KY). Polar sites (KY) can also function as pigment adsorption groups.

<Polar site (KY)>
The resin-type dispersant used in the present invention has a polar site (KY) in a part of its structure.
This polar site (KY) is expected to have the following actions (1) to (3).
(1) Becomes an adsorption group to the pigment and stabilizes the dispersion. Contributes to viscosity stability (2) When a pigment derivative is included, it forms a salt with an adsorbent having a pigment adsorption group to stabilize dispersion. Contributes to viscosity stability. (3) Maintains an appropriate amount of water, and when used as a colored composition, improves sensitivity and increases development speed.

The polar moiety (KY) is not particularly limited as long as it forms a salt with the pigment or pigment derivative. and basic functional groups such as tertiary amino groups.

The portion other than the polar portion (KY) of the dispersant is not particularly limited as long as it has affinity for the solvent, and examples thereof include alkyl chains, polyesters, polyamides, polyurethanes, polyethers, vinyl polymers and the like. , a polyester or a vinyl polymer is particularly preferable from the viewpoint of ease of synthesis and ease of control of solvent affinity.

As a combination with a pigment derivative, when the pigment derivative is an acidic derivative, the polar site (KY) of the resin-type dispersant has good basicity, and when the pigment derivative is a basic derivative or a basic vinyl resin, a resin-type dispersant is used. The polar portion (KY) of the dispersant should be acidic.
Resin-type dispersants are classified into straight-chain ones in which the main chain is not branched and those in which the main chain is branched. In addition, regardless of whether or not the main chain is branched, a polymer side chain (portion other than the main chain) may be modified to extend the side chain (hereinafter also referred to as a comb shape).

<Resin type dispersant having a polar site (KY) at the end>
A resin-type dispersant having a polar site (KY) at its terminal is prepared by preparing a polymer with a polymerization initiator having a polar site, or synthesizing a polymer having a functional group at its terminal in advance, and modifying the functional group into a polar site. method.
All linear polymers can be produced using known methods. It can be synthesized using a known method such as As an example of a method for modifying the polar site of the resin-type dispersant, a dispersant having a polar site (KY) as a carboxyl group is prepared by using a vinyl polymer having one hydroxyl group at one end as a raw material and adding an aromatic tricarboxylic acid. It can be produced by adding an anhydride (Y1) to a hydroxyl group.

The number-average molecular weight of the resin type dispersant refers to the molecular weight of the entire vinyl polymer obtained by adding the aromatic tricarboxylic anhydride (Y1) to the hydroxyl group in the above production method, for example.

<Resin type dispersant having a polar site (KY) other than the terminal>
All resin-type dispersants having a polar site (KY) other than the terminal can be produced using a known method. can be synthesized using a known method. As an example of a method for producing a resin-type dispersant having a polar site (KY) other than the terminal, a dispersant whose polar site (KY) is a carboxyl group is prepared using a vinyl polymer having two hydroxyl groups at one end as a raw material. , can be produced by adding an aromatic tetracarboxylic dianhydride (Y2) to a hydroxyl group.

The number average molecular weight of the side chain in the resin-type dispersant having a polar site (KY) other than the terminal refers to, for example, the molecular weight of the vinyl polymer having two hydroxyl groups at one terminal in the above production method.
Moreover, a special site such as a hydroxyl group, an ethylenically unsaturated double bond, an epoxy group, or an oxetane group may be added to the side chain portion by a known method.

In the resin-type dispersant used in the present invention, it is preferable that the polar site (KY) is a carboxyl group, and a polymer (X) having a hydroxyl group at one end and an aromatic tetracarboxylic dianhydride (Y2) are combined. A dispersant having an aromatic carboxyl group to be reacted is preferred.

All polymers (X) having a hydroxyl group at one end can be produced using known methods. For example, it can be obtained by mixing a compound having a hydroxyl group and a thiol group in the molecule with an ethylenically unsaturated monomer and heating by the method described in JP-A-2009-251481.

Compounds having a hydroxyl group and a thiol group in the molecule include, for example, mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, and 2-mercapto-3-butanol, 1 -mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto -2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3 -propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

(Aromatic tricarboxylic anhydride (Y1))
Examples of the aromatic tricarboxylic anhydride (Y1) include 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.

(Aromatic tetracarboxylic dianhydride (Y2))
The aromatic tetracarboxylic dianhydride (Y2) includes pyromellitic dianhydride, ethylene glycol dianhydride trimellitic ester, propylene glycol dianhydride trimellitic ester, butylene glycol dianhydride trimellitic ester, 3, 3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetra Carboxylic 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)diphenyl Propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenyl Phosphine 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'-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-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1 , 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and the like.

[Other resin-type dispersants]
The present invention may further contain other resin-type dispersants.
Other resin-type dispersants have a colorant-affinity site that has the property of adsorbing to the additive colorant and a site that is compatible with the colorant carrier. Including those overlapping with the above, specifically, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid Acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) Oil-based dispersants such as amides and their salts formed by the reaction of polyesters with free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers Water-soluble resins such as coalescence, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphate esters, etc. are used, and these can be used alone or in combination of two or more.
Examples of the resin-type dispersant having a basic functional group include nitrogen atom-containing graft copolymers and nitrogen atom-containing agents having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include acrylic block copolymers and urethane resin type dispersants.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Lubrizol Japan, １３６５０、１３９４０、１６０００、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２５５０、３３５００、３２６００、３４７５０、３５１００、３６６００、３８５００、４１０００、４１０９０、５３０９５、５５０００、 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824 and the like.

The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass, more preferably in an amount of about 10 to 100% by mass, based on the total amount of the pigment.

<Pigment derivative>
A pigment derivative can be used in the coloring composition of the present invention for the purpose of improving pigment dispersibility. Pigment derivatives used in the present invention include diketopyrrolopyrrole derivatives, benzoisoindole derivatives, anthraquinone derivatives, dianthraquinone derivatives, thiazineindigo derivatives, azo pigment derivatives, quinophthalone derivatives, and quinacridone derivatives. Examples of the structure of the pigment derivative include, but are not limited to, pigment derivatives represented by the following formula (4).

P−Lm formula (4)

[In formula (4),
P is a diketopyrrolopyrrole residue, a benzoisoindole residue, an anthraquinone residue, a dianthraquinone residue, a thiazineindigo residue, an azo dye residue, a quinophthalone residue, or a quinacridone residue;
m is an integer from 1 to 4,
L each independently represents -OH; -SO ₃ H, -COOH, 1 to 3 of these acidic groups;
phthalimidomethyl group which may have a substituent; represented by the following formulas (a), (b), (c), (d), (e), or (f) is a group that
X is _-SO2- , _{-CO- , -CH2-} , _-CH2NHCOCH2- , _{-CH2NHSO2CH2-} , or a direct bond _;
Y is -NH-, -O-, -S-, or a direct bond;
n is an integer from 1 to 10,
R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ¹⁶ and R ¹⁷ together are an optionally substituted heterocyclic ring containing an additional nitrogen, oxygen, or sulfur atom;
R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted carbon atom is an alkenyl group having a number of 2 to 20,
R ²³ is a substituent represented by formula (a) or formula (b),
R ²⁴ is a chlorine atom, —OH, an alkoxyl group, or a substituent represented by formula (a) or formula (b);
Z is -CONH-, -NHCO-, -SO ₂ NH-, or -NHSO ₂ -;
R ²⁵ is a hydrogen atom, —NH ₂ , —NHCOCH ₃ , —NHR ²⁶ , or a substituent represented by formula (c), wherein R ²⁶ may have a substituent and may have 1 to 1 carbon atoms. 20 alkyl groups, and optionally substituted alkenyl groups having 2 to 20 carbon atoms. ]

Monovalent to trivalent metals include sodium, potassium, magnesium, calcium, iron, aluminum, and the like. Examples of alkylammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, or stearylamine, or palmityltrimethylammonium salts, dilauryldimethylammonium salts, distearyldimethylammonium salts, and the like. A quaternary alkylammonium salt is mentioned.

A phthalimidomethyl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a heterocyclic substituent which may have a substituent, , a halogen atom, a nitro group, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, an alkoxyl group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms.
Examples include, but are not limited to, 20 alkylthio groups and the like.

The pigment derivative is subjected to a sulfonation reaction by heating in sulfuric acid or fuming sulfuric acid, a phthalimidomethylation reaction by dehydration condensation with N-hydroxymethylphthalimide in sulfuric acid, chlorosulfonation using chlorosulfonic acid and thionyl chloride, It is synthesized by a known production method such as a sulfonamidation reaction in which an amine component such as dimethylaminopropylamine is reacted.

Examples of the amine component used to form the substituents represented by the above formulas (a), (b) and (c) include dimethylamine, diethylamine, methylethylamine, N,N-ethyl Isopropylamine, N,N-ethylpropylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisopropylamine, dipropylamine, N , N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N,N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di(2-ethylhexyl ) amine, dioctylamine, N,N-methyloctadecylamine, didecylamine, diallylamine, N,N-ethyl-1,2-dimethylpropylamine, N,N-methylhexylamine, dioleylamine, distearylamine, N,N -dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminoamylamine, N,N-dimethylaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N- Diethylaminohexylamine, N,N-diethylaminobutylamine, N,N-diethylaminopentylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminopropylamine, N,N-dibutylaminoethylamine, N,N-dibutyl aminobutylamine, N,N-diisobutylaminopentylamine, N,N-methyl-laurylaminopropylamine, N,N-ethyl-hexylaminoethylamine, N,N-distearylaminoethylamine, N,N-dioleylaminoethylamine , N,N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotinic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl- 2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1 -Cyclopentylpiperazine and the like, but are not limited to these.

Further, when a substituent is introduced into the azo dye, the azo pigment derivative can be produced by previously introducing the substituent into the diazo component or the coupling component and then conducting the coupling reaction.

Pigment derivatives can be used by mixing the diketopyrrolopyrrole-based micronized pigment with the micronized pigment when dispersing it in a pigment carrier. A method of adding at the time of milling treatment is mentioned. The method of mixing the pigment derivative in water or an organic solvent during the production of the pigment and the method of adding it during the salt milling treatment exhibit the effect of suppressing the crystal growth of the diketopyrrolopyrrole pigment, but the effect of suppressing the crystal growth In order to exhibit the above, it is required that the pigment derivative efficiently adsorbs to the surface of the diketopyrrolopyrrole pigment and does not easily desorb. Therefore, in many cases, the structure of the pigment derivative partially has a chemical structure similar to that of the pigment used. For this reason, pigment derivatives having a diketopyrrolopyrrole structure, a thiazineindigo structure, a benzoisoindole structure, or a quinacridone structure are generally effective when producing a diketopyrrolopyrrole pigment. be.

Moreover, when a pigment derivative is used, it is necessary not to impair the color tone of the composition containing the diketopyrrolopyrrole pigment as much as possible. From the viewpoint of hue, it is preferable to use a diketopyrrolopyrrole derivative, a benzoisoindole derivative, a thiazineindigo derivative, an azo pigment derivative, or a quinophthalone derivative exhibiting a yellow or orange color.

The amount of the pigment derivative to be blended is preferably in the range of 0.5 to 40 parts by mass with respect to 100 parts by mass of the composition containing the diketopyrrolopyrrole pigment. More preferably, it is in the range of 3 to 35 parts by weight per 100 parts by weight of the diketopyrrolopyrrole micronized pigment.
This is because when the amount is more than 0.5 parts by mass, a sufficient crystal growth suppressing effect is obtained, and when the amount is less than 40 parts by mass, it is easy to obtain a good color tone of the diketopyrrolopyrrole pigment.

Specific examples of the pigment derivative used in the present invention are described below, but the present invention is not limited thereto.

(Specific examples of diketopyrrolopyrrole derivatives)
Examples of diketopyrrolopyrrole derivatives include compounds represented by the following formula (5) or (6).

(Specific examples of benzoisoindole derivatives)
Benzoisoindole derivatives include, for example, compounds represented by the following formula (7).

(Specific examples of anthraquinone derivatives)
Examples of anthraquinone derivatives include compounds represented by the following formula (8).

(Specific examples of dianthraquinone derivatives)
The dianthraquinone derivative includes, for example, compounds represented by the following formula (9).

(Specific examples of thiazineindigo derivatives)
Thiazine indigo derivatives include, for example, compounds represented by the following formula (10).

(Specific examples of azo pigment derivatives)
Examples of the azo pigment derivative include compounds represented by the following formula (11), formula (12), or formula (13).

(Specific examples of quinophthalone derivatives)
Examples of quinophthalone derivatives include compounds represented by the following formulas (14-1) to (14-13).

(Specific examples of quinacridone derivatives)
Examples of quinacridone derivatives include compounds represented by the following formula (15).

(Average primary particle size of pigment)
The pigment composition of the present invention is required to have a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution. The average primary particle size of the pigment composition of the present invention as determined by TEM (transmission electron microscope) is preferably in the range of 5 to 70 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent. Moreover, if it becomes larger than 70 nm, it will become impossible to obtain sufficient contrast ratio. For these reasons, a more preferred range is 10 to 40 nm. When the pigment is synthesized and mixed to form a pigment composition, if the average primary particle size is within the above range, it may be used as it is. And it is desirable to perform grain size regulation.

(Refinement of pigment)
The diketopyrrolopyrrole-based pigment of the present invention is preferably used after being finely divided, and salt milling treatment is preferable as the method for making finely divided.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. This is a treatment in which water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water after kneading to a certain extent. The water-soluble inorganic salt acts as a crushing aid, and during salt milling, the high hardness of the inorganic salt is used to crush the pigment, which is thought to generate an active surface and cause crystal growth. there is Therefore, during kneading, crushing and crystal growth of the pigment occur at the same time, and the primary particle size of the pigment obtained differs depending on the kneading conditions.

In order to promote crystal growth by heating, the heating temperature is preferably 35 to 150°C. If the heating temperature is lower than 35° C., crystal growth does not occur sufficiently and the shape of the pigment particles becomes nearly amorphous, which is not preferable. On the other hand, if the heating temperature exceeds 150° C., crystal growth proceeds excessively and the primary particle size of the pigment becomes large, which is not preferable as a colorant for color filters. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling pigment and the cost required for the salt milling treatment.

By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt used for the salt milling treatment, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, most preferably 300 to 1,200 parts by mass, based on 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent has a function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety.

Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Used. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, most preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

In the salt milling treatment, a pigment derivative may be used in combination to improve kneading efficiency, which is very effective in making the pigment finer and granulating it. In the miniaturization of the diketopyrrolopyrrole pigment used in the present invention, it is preferable to use the above pigment derivative, but the invention is not limited thereto. The pigment derivative is preferably used in an amount that does not affect the color tone, that is, in the range of 0.5 to 40 parts by weight per 100 parts by weight of the pigment.

Moreover, when performing a salt milling process, you may add resin as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resins used are preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the above organic solvents. The amount of the resin used is preferably in the range of 5 to 200 parts by weight per 100 parts by weight of the pigment.

The diketopyrrolopyrrole pigment of the present invention can be used as a coloring composition by using it together with a binder resin and an organic solvent. Also, a coloring agent other than the composition containing the diketopyrrolopyrrole pigment of the present invention may be used in combination.

<Other pigments>
For the colorant used in the present invention, a pigment other than the pigment containing the compound represented by the general formula (1) or (2) is used in combination in order to adjust the chromaticity or the like within a range that does not impair the effects of the present invention. You may These pigments can be used singly or as a mixture of two or more at any ratio as required.

Other pigments include, for example, C.I. I. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287 and other red pigments.

Also, C.I. I. an orange pigment such as Pigment Orange 43, 71, or 73 and/or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 1
5, 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, 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221 or any of the following A yellow pigment represented by formula (3) can be used in combination.

Preferable pigments to be used in combination are azo, naphthol azo, diketopyrrolopyrrole, anthraquinone, quinophthalone, and perylene pigments from the viewpoint of fastness such as heat resistance and light resistance and chromaticity range. mentioned. Specifically, C.I. I. Pigment Red 269, 177, 254, 242, C.I. I. Pigment Yellow 138, 139, 150, 185, yellow pigments represented by the following general formula (16), and brominated diketopyrrolopyrrole pigments.
In this specification, C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I
. Pigment Yellow 150 and one or more selected from the group consisting of yellow pigments represented by the following general formula (16) are preferably included. This further improves the brightness and tinting strength.

general formula (16)

[In general formula (16), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or a substituent an aryl group, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups which may have substituents, or substituents of these acidic groups; A sulfamoyl group which may be present is shown.
Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may combine to form an aromatic ring which may have a substituent.

Here, halogen atoms include fluorine, chlorine, bromine and iodine.

Examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group and n-octyl. linear or branched alkyl groups such as groups, stearyl groups, 2-ethylhexyl groups, trichloromethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 2,2-dibromoethyl groups, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4- Alkyl groups having substituents such as a methoxybenzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group can be mentioned.

Examples of the alkoxyl group which may have a substituent include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3 -Dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group and other linear or branched alkoxyl groups, trichloromethoxy group, trifluoromethoxy group, 2 , 2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group and alkoxyl groups having substituents such as benzyloxy groups.

In addition, the aryl group which may have a substituent includes a phenyl group, a naphthyl group, an anthranyl group and the like, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group and 2-aminoanthraquinonyl group.

Examples of acidic groups include --SO ₃ H and --COOH.
Valid metal salts include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts and the like. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine; quaternary alkyl salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts; Ammonium salts are mentioned.

_{The " substituent _ _ _} ” includes the above halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, and the like.

Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ in general formula (16) may combine together to form an aromatic ring which may have a substituent. The aromatic ring referred to herein includes aromatic hydrocarbon rings and heteroaromatic rings. Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, and phenanthrene rings. Examples of heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, carbazole ring and the like.

Specific examples of the yellow pigment represented by the general formula (16) used in the colorant for color filters of the present invention include quinophthalone compounds (a) to (r) shown below. It is not limited. Moreover, the quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited thereto.

<Dye (a)>
In this specification, the dye (a) is preferably one or more selected from the group consisting of xanthene, dipyrromethene, triarylmethane, cyanine, phthalocyanine and anthraquinone dyes.
The coloring composition of the present invention uses a dye together with the diketopyrrolopyrrole pigment. Any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like can be used as dyes. Moreover, it may be in the form of a derivative of these or a lake pigment obtained by turning a dye into a lake.

Furthermore, in the case of acid dyes having an acidic group such as sulfonic acid or carboxylic acid, or in the form of direct dyes, inorganic salts of acid dyes, acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or a salt-forming compound using a resin component having these functional groups, or a sulfonamidation and use as a sulfonic acid amide compound. In order to be excellent in resistance, it is possible to make a coloring composition excellent in fastness, which is preferable.
In addition, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in its side chain.

In the case of the form of a basic dye, it can be used by forming a salt using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. An anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acid dye can be used. It is more preferable.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be excellent in resistance, which is preferable.

Chemical structures of dyes include, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthra pyridone dyes, etc.), carbonium dyes (diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, Examples include dye structures derived from dyes selected from indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and metal complex dyes thereof.

Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triarylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium Xanthene dyes, cyanine dyes, triarylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanines. A dye structure derived from a dye selected from the group of dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in "Shinban Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), "Dye Handbook" (Ogawara et al.). Ed.; Kodansha, 1986).

[Xanthene dye]
Xanthene dyes that can be preferably used in the present invention exhibit red or purple color, and are preferably in the form of oil-soluble dyes, acid dyes, direct dyes, or basic dyes. Alternatively, it may be in the form of a lake pigment obtained by converting these dyes into a lake.
Among these, xanthene-based oil-soluble dyes and xanthene-based acid dyes are preferably used because they are excellent in hue.

Exhibiting red and purple means C.I. I. Solvent Red, C.I. I. oil-soluble dyes such as solvent violet; I. Basic Red, C.I. Basic dyes such as I. basic violet, C. I. Acid Red, C.I. I. acid dyes such as acid violet; I. Direct Red, C.I. I. Direct dyes such as direct violet.
Here, the direct dye has a sulfonic acid group (--SO ₃ H, --SO ₃ Na) in its structure,
For the purposes of the present invention, direct dyes are considered to be acid dyes.

Moreover, it is preferable to use the xanthene-based basic dye after salt formation using an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use naphthalenesulfonic acid such as Tobias acid and perchloric acid in terms of resistance. More specifically, the xanthene dye is preferably a salt forming compound of a xanthene acid dye having an anionic group and a resin having a cationic group in its side chain.
In addition, xanthene-based acid dyes are used as salt-forming compounds by salting using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and resin components having these functional groups. or sulfonamidated to be used as a sulfonic acid amide compound is preferred from the standpoint of resistance.

Among these, salt-forming compounds of xanthene-based acid dyes and/or sulfonic acid amide compounds of xanthene-based acid dyes are particularly preferable because they are excellent in hue and resistance. and a sulfonic acid amide compound obtained by sulfonamidating a xanthene-based acid dye.

Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and durability.

The form of the dye used in the present invention will be specifically described below.

[Xanthene oil-soluble dye]
Xanthene oil-soluble dyes include C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C.I.
C.I. Solvent Red 140, C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2, C.I.
Among them, C.I. Solvent Red 35, C.I.
I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 10
9, C.I. Solvent Red 237, C.I. Solvent Red 246, and C.I. Solvent Violet 2 are more preferred.

[Xanthene-based basic dye]
Examples of xanthene-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6GCP)
, 8 (Rhodamine G), C.I. and I. Basic Violet 10 (Rhodamine B). Among them, C.I. I. Basic Red 1, C.I. I. Basic Violet 10 is preferably used.

[Xanthene acid dye]
Examples of xanthene-based acid dyes include C.I. I. Acid Red 51 (erythrosine (food red No. 3)), C.I. I. Acid Red 52 (acid rhodamine), C.I. I. Acid Red 87 (Eosin G (Edible Red No. 103)), C.I. I. Acid Red 92 (Acid Phloxine PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferred to use Acid Violet 9.
Among them, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388, or C.I., which is a rhodamine acid dye. I. Acid Red 52 (acid rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. More preferably, Acid Violet 9 is used.
Among these, C.I. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

In addition, these acid dyes are preferably salt-forming compounds of acid dyes and nitrogen-containing compounds, such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, and functional compounds thereof. A resin component having a group is used to form a salt to form a salt-forming compound of a xanthene-based acid dye, which is preferable because high heat resistance, light resistance, and solvent resistance can be imparted.
Moreover, it may be a salt-forming compound of an acid dye and a compound having an onium base. An excellent coloring composition can be obtained.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, hardened beef tallow alkylamine, aliphatic unsaturated primary amines such as allylamine, aniline, benzylamine, and the like. .

Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine and diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl amines, di-cured beef tallow alkylamines, distearylamines, etc.

Tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

Quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, and dioctyldimethylammonium chloride. , monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride, benzyldimethylstearylammonium chloride, and Examples include benzyldimethyloctylammonium chloride, dialkyl (alkyl is C14 to C18) dimethylammonium chloride (cured beef tallow), and the like.

Specific products of quaternary ammonium salt compounds include, for example, Kotamine 24P, Kotamine 86P Conc, Kotamine 60W, Kotamine 86W, Kotamine D86P, Sansol C, Sansol B-50 manufactured by Kao Corporation, and Arcade 210- manufactured by Lion Corporation. 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, among others, Cortamine D86P (distearyldimethylammonium chloride), Arcade 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

[Resin having cationic group in side chain]
A resin having a cationic group in a side chain will be described. The resin having a cationic group in the side chain for obtaining the salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and considering storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are preferred. is more preferable. Ammonium salts are more preferred.

The resin having a cationic group in the side chain is an alkali resin containing a structural unit represented by the following general formula (17), wherein the cationic group in general formula (17) is an anionic group and a salt of a xanthene-based acid dye. By forming, a salt-forming compound can be obtained.

[In general formula (17), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted ^alkenyl group, or an optionally substituted aryl group ^; Two of them may combine with each other to form a ring. Q represents an alkylene group, an arylene group, --CONH--R ⁵⁵ --, --COO--R ⁵⁵ --, and R ⁵⁵ represents an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

[salt formation]
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in a side chain can be produced by a conventionally known method. A specific technique is disclosed in Japanese Unexamined Patent Application Publication No. 11-72969.
As an example using a xanthene-based acid dye, after dissolving the xanthene-based acid dye in water, a quaternary ammonium salt compound may be added, and the salt-forming treatment may be performed while stirring. Here, the sulfonic acid group (--SO ₃ H) and the sodium sulfonate group (--S
A salt-forming compound is obtained in which the portion of O ₃ Na) and the portion of the ammonium group (NH ₄ ⁺ ) of the quaternary ammonium salt compound are combined. In place of water, methanol and ethanol are also usable solvents for chlorination.

The salt-forming compound used in the present invention is obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by general formula (17) and an acid dye is dissolved, or can be easily obtained by mixing an aqueous solution of a resin having a cationic group in its side chain and an aqueous solution of an acid dye under stirring or shaking. In an aqueous solution, the ammonium group of the resin and the anionic group of the acid dye are ionized, and they form an ionic bond, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain and the acid dye used may be of a single type or may be of a plurality of types having different structures.
Also, with other acid dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as for xanthene dyes.

[Sulfonic acid amide compound]
The acid dye used in the present invention may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
Sulfonic acid amide compounds of acid dyes that can be preferably used in the acid dyes of the present invention are obtained by chlorinating acid dyes containing --SO ₃ H and --SO ₃ Na in a conventional manner to convert --SO ₃ H to --SO ₂ Cl. and this compound can be prepared by reaction with an amine having a --NH ₂ group.
Amine compounds that can be preferably used in sulfonamidation include, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-(2-ethylhexyloxy)propylamine, and 3-ethoxypropyl. Amines, cyclohexylamines and the like are preferably used.
As an example of xanthene-based acid dyes, C.I. I. When obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 289 was sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 289 may be obtained.
Also, C.I. I. In the case of obtaining a sulfonic acid amide compound by modifying Acid Red 52 with 3-(2-ethylhexyloxy)propylamine, C.I. I. Acid Red 52 is sulfonyl chlorided and then reacted with the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to give C.I. I. A sulfonic acid amide compound of Acid Red 52 may be obtained.
Also, with other acid dyes, sulfonic acid amide compounds can be obtained in the same manner as with xanthene dyes.

Examples of such xanthene-based dyes include JP-A-2010-032999, JP-A-2011-138094, JP-A-2011-227313, JP-A-2011-242752, JP-A-2012-107192, JP 2013-033194, JP 2011-71888, JP 2013-72263, JP 2013-81209, JP 2014-173064, JP 2013-53028, JP 2013 -52186, JP 2014-196392, JP 2014-196393, JP 2014-201714, JP 2014-201715, JP 2013-050693, JP 2013-178478 No. 2013-203956, International Publication No. 2013/011687 pamphlet, etc. can be used.

[Dipyrromethene dye]
The dipyrromethene dye is a dye that has a partial structure derived from a dipyrromethene dye as a partial structure of the dye site, and is preferably a dipyrromethene compound, or a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal, or a metal compound, especially. However, a metal complex compound in which the structure represented by the general formula (5) is coordinated to a metal atom or a metal compound (hereinafter referred to as “dipyrromethene metal complex compound” as appropriate) is preferable.

[Dipyrromethene metal complex compound]
A metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (18) is coordinated to a metal atom or a metal compound will be described.

In general formula (18), R ⁶¹ to R ⁶⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁶⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. represents
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, such as a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal valence metal chlorides. Examples of metals or metal compounds include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., as well as AlCl ₃ , InCl ₃ , FeCl ₃ , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, and Si(OH) ₂ and other metal hydroxides.
Among these, as metals or metal compounds, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO is more preferred, Fe, Zn, Cu, Co, B or VO is most preferred.

Examples of such dipyrromethene dyes include Japanese Patent No. 5085256, Japanese Patent Application Laid-Open No. 2008-292970, Japanese Patent Application Laid-Open No. 2010-85758, Japanese Patent Application Laid-Open No. 2010-84009, Japanese Patent Application No. 2010-43530, and Japanese Patent Application Laid-Open No. 2013. -080010, JP-A-2013-210596, International Publication No. 2013/141156 pamphlet, etc. can be used.

Here, the dipyrromethene dye in the colorant used in the present invention is preferably a dipyrromethene dye that has an absorption maximum near 500 to 600 nm, and absorbs near 525 to 575 nm, from the viewpoint of improving the brightness and contrast ratio of the color filter. A dipyrromethene dye having a maximum is more preferred, and a dipyrromethene dye having an absorption maximum near 540 to 560 nm is particularly preferred.

Examples of such dipyrromethene dyes include exemplary compound I-1 (absorption maximum 558.2 nm) and III-45 (absorption maximum 546.7 nm) described in Japanese Patent No. 5,085,256.

[Triarylmethane Dyes]
Examples of the triarylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosolic acid dye skeleton having an OH group.
A triaminotriphenylmethane-based dye skeleton is preferable in terms of excellent color tone and superior lightfastness to other dyes. Among these, a diphenylnaphthylmethane dye skeleton, which is a basic dye, is particularly preferred.

[Triarylmethane-based basic dye]
A triarylmethane-based basic dye develops color by oxidation of an NH ₂ or OH group para to the central carbon to form a quinone structure.
They are classified into the following three types depending on the number of NH ₂ and OH groups. Among them, triaminoarylmethane-based basic dyes are preferable in terms of developing good blue, red and green colors.
a) diaminotriphenylmethane-based basic dyes b) triaminotriphenylmethane-based basic dyes c) rosolic acid-based basic dyes having an OH group triaminotriphenylmethane-based basic dyes, diaminotriphenylmethane-based basic dyes Dyes are preferred because they have a vivid color tone and are superior to other dyes in light fastness.

Blue-based triarylmethane-based basic dyes have spectral characteristics with high transmittance in the range of 400 to 440 nm, so that high brightness can be obtained especially when used for forming blue filter segments. It is preferable because it can

Specific examples of triarylmethane-based basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), Basic Violet 3 (Crystal Violet), Basic Violet 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), Basic Blue 5 (Basic Cyanine EX), Basic Blue 7 (Victoria Pure Blue BO), Basic Blue 26 (Victoria Blue B
conc.), C.I. Examples include I. Basic Green 1 (Brilliant Green GX) and Basic Green 4 (Malachite Green).
Among them, C.I. I. Basic Blue 7 is preferably used.

Moreover, in the case of a triarylmethane-based basic dye, it can be used after chlorination using an organic acid, perchloric acid, or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferable because of their excellent resistance and compatibility with pigments. An anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acid dye can be used. It is more preferable.

Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, aromatic carboxylic acids, organic carboxylic acids such as fatty acids, Alternatively, it has the form of an acid dye. Or they may be metal salts thereof. Moreover, a salt-forming compound with a resin having an acid group is also preferable.

[salt formation]
Salt-forming compounds of these basic dyes and anionic counters can be synthesized by conventionally known methods. A specific technique is disclosed in Japanese Unexamined Patent Application Publication No. 2003-215850.
For example, after dissolving a triarylmethane-based basic dye in water, an organic sulfonic acid or (organic sodium sulfonate) solution may be added, and chlorination may be performed while stirring. Here, a salt-forming compound is obtained in which the amino group (--NHC ₂ H ₅ ) portion of the triarylmethane-based basic dye and the sulfonic acid group (--SO ₃ H) portion of the organic sulfonic acid are combined.
Here, the organic sulfonic acid can also be dissolved in an alkaline solution such as sodium hydroxide and used in the form of sodium sulfonate (--SO ₃ Na) before salt formation. In the present invention, a sulfonic acid group (--SO ₃ H) and a functional group that is sodium sulfonate (
—SO ₃ Na) is also synonymous.

Examples of such triarylmethane-based dyes include JP-A-2002-014222, JP-A-2003-246935, JP-A-2003-246935, JP-A-2008-304766, and JP-A-2010-256598. , JP 2011-200560, JP 2011-186043, JP 2012-173399, JP 2012-233033, JP 2012-098522, JP 2012-288970, JP Application No. 2012-200469, JP 2014-196262, International Publication No. 2010/123071, International Publication No. 2011/162217, International Publication No. 2013/108591, etc. can be used.

[Cyanine dye]
As the cyanine dye, any compound having a dye moiety containing a cyanine skeleton in the molecule can be used without limitation.
Examples of cyanine dyes include C.I. I. basic yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic Violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic Orange 27, 42, 44, 46, C.I. I. Basic Blue 62, 63 and the like.
In addition, cyanine dyes described in JP-A-2014-224970, JP-A-2013-261614, etc. can also be used.

[Anthraquinone Dyes]
Anthraquinone dyes are dyes having an anthraquinone skeleton in the molecule.
Examples of anthraquinone dyes include C.I. I. Solvent Yellow 117, 163, 167, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse Violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Mordan Tread 3, 11, C.I. I. Mordant Blue 8 and the like can be mentioned. In addition, the anthraquinone dyes described in JP-A-9-291237, WO 2003/080734, WO 2006/024617, 2011-174987, 2013-53273, etc. It can be used as a known technique. The anthraquinone dye preferably dissolves in an organic solvent, more preferably a blue, violet or red anthraquinone dye. Examples of anthraquinone dyes include C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent Blue 122 is preferable from the viewpoint of brightness and contrast ratio.

When used in combination with the red pigment, yellow pigment, orange pigment, or dye, the content of the pigment containing the compound represented by the chemical formula (1) or general formula (2) is 10 to 90% by mass, preferably 20 to 80% by mass. If the content of the pigment containing the compound represented by the above chemical formula (1) or general formula (2) is less than 10% by mass, the excellent effect of brightness and coloring power cannot be exhibited sufficiently.

<Binder resin (B)>
The coloring composition of the present invention contains a binder resin (B). As the binder resin (B), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm is used. Binder resins are classified into thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc., when classified according to their main curing methods, and active energy ray-curable resins are thermoplastic resins. It may be a resin or one having a thermosetting function, and an alkali-soluble resin is preferable from the viewpoint of developability. It may also contain a thermoplastic resin that is not curable with active energy rays, and it is also preferably alkali-soluble. These can be used alone or in combination of two or more.

The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass based on the total weight of the colorant (100 parts by mass). It is preferably used in an amount of 20 parts by mass or more because of good film formability and resistance, and is preferably used in an amount of 400 parts by mass or less because it has a high colorant concentration and can exhibit good color characteristics. .

(Thermoplastic resin)
Thermoplastic resins that can be used as the binder resin (B) include, for example, acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylenes, chlorinated polypropylenes, polyvinyl chlorides, vinyl chloride-vinyl acetate copolymers, Polymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and A polyimide resin etc. are mentioned.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfone groups. Specific examples of resins include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/ (anhydrous) maleic acid copolymer and the like. Among them, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly alkali-soluble resins having acidic groups and/or hydroxyl groups, has good developability, heat resistance, and transparency. Since it is high, it is preferably used.

(alkali-soluble resin)
The colored composition of the present invention preferably contains an alkali-soluble resin in terms of developability, heat resistance and transparency. It is for imparting development solubility in the alkali development process during color filter production, and has an acid group and/or a hydroxyl group. Moreover, in order to further improve the photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

(Alkali-soluble resin having an ethylenically unsaturated double bond)
The alkali-soluble resin contained in the coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond has been introduced by the method (i), (ii) or (iii) shown below, when forming a coating film by exposure to active energy rays, the resin is 3 Dimensional cross-linking increases cross-linking density and improves chemical resistance.

[Method (i)]
As method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. , The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate. , and 3,4-epoxycyclohexyl (meth)acrylate, 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 (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like are mentioned, and 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, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

As a method analogous to method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and another unsaturated monobasic acid monomer having a carboxyl group or another monomer is copolymerized. There is a method of reacting the side chain hydroxyl groups of the resulting copolymer with the isocyanate groups of an ethylenically unsaturated monomer having an isocyanate group.

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

Ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. However, without being limited to these, two or more kinds can be used together.

Monomers constituting the alkali-soluble resin include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as acrylamides styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine,
Compounds represented by the following general formula (19), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenolic ethylene oxide (EO)-modified (meth)acrylate , EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, and PO-modified (meth)acrylates of nonylphenol.

general formula (19)

(In general formula (19), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon atom optionally having a benzene ring. an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

A carboxyl group-containing ethylenically unsaturated monomer can also be used. Carboxyl group-containing ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

A hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of hydroxyl group-containing ethylenically unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-
Hydroxybutyl (meth)acrylate or hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate can be mentioned. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone , and/or (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added.

Phosphate ester group-containing ethylenically unsaturated monomers can also be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide and polyphosphoric acid. is mentioned.
[Method (iii)]
As method (iii), an unsaturated ethylenic double bond can be introduced by copolymerizing a side chain type cyclic ether-containing monomer and one or more other monomers.
The side chain type cyclic ether-containing monomer is, for example, an unsaturated compound containing at least one skeleton selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
The tetrahydrofuran skeleton includes tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, (meth)acrylic acid tetrahydrofuran-3-yl ester;
As the furan skeleton, 2-methyl-5-(3-furyl)-1-penten-3-one, furfuryl (meth)acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan -2-butyl-3-methoxy-3-en-2-one, 6-(2-furyl)-2-methyl-1-hexene-3-one, 6-furan-2-yl-hex-1-ene -3-one, 2-furan-2-yl-1-methyl-ethyl acrylate, 6-(2-furyl)-6-methyl-1-hepten-3-one and the like;
As the tetrahydropyran skeleton, (tetrahydropyran-2-yl)methyl methacrylate, 2,6-dimethyl-8-(tetrahydropyran-2-yloxy)-oct-1-en-3-one, tetrahydropyran 2-methacrylate -2-yl esters, 1-(tetrahydropyran-2-oxy)-butyl-3-en-2-one and the like;
As the pyran skeleton, 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrone, 4-(1,5-dioxa-6-oxo-7-octenyl)-6 -methyl-2-pyrone and the like;
As the lactone skeleton, 2-methyl-tetrahydro-2-oxo-3-furanyl 2-propenoate, 2-methyl-7-oxo-6-oxabicyclo[3.2.1]oct-2-propenoate, 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-7-yl ester of 2-propenoic acid, 2-methyl-tetrahydro-2-oxo-2-propenoic acid 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro[3,2-b]- 6-yl ester, 2-methyl-2-propenoic acid 2-(tetrahydro-5-oxo-3-furanyl)ethyl ester, 2-methyl-decahydro-8-oxo-5,9-methano-2H 2-propenoic acid -furo[3,4-g]-1-benzopyran-2-yl ester, 2-methyl-2-[(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan 2-propenoate -6-yl)oxy]ethyl ester, 2-propenoic acid 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl)oxy]propyl ester, 2-propenoic acid 2-methyl-2-oxy-1 -oxaspiro[4.5]dec-8-yl ester and the like. Among these, tetrahydrofurfuryl (meth)acrylate is preferred from the viewpoint of coloration, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

(Alkali-soluble resin having no ethylenically unsaturated double bond)
The coloring composition of the present invention may contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating film. Synthesized using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and by not imparting an ethylenically unsaturated bond to the side chain, ethylene Alkali-soluble resins having no polyunsaturated double bonds can be obtained.

The alkali-soluble resin in the present invention preferably has 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.

The weight-average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, in order to impart alkali developing solubility, and 4,000 More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, the adhesiveness to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is 50 to impart alkali developing solubility.
200 or less (KOHmg/g), preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

<Thermosetting compound>
The present invention can further contain a thermosetting compound. When producing a color filter using the coloring composition for a color filter of the present invention, by containing a thermosetting compound, it reacts during baking of the filter segment and increases the crosslink density of the coating film, so that the heat resistance of the filter segment is improved. As a result, pigment agglomeration during baking of the filter segment is suppressed, and the effect of improving the contrast ratio is obtained.

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

(epoxy compound)
The epoxy compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxy benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol , biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) and polycondensates, polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine-based epoxy resins , glycidyl ester-based epoxy resins, etc., but are not limited to these as long as they are commonly used epoxy compounds. These may be used independently and may use 2 or more types.

Commercially available products include, for example, Epicoat 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, and Epicote 1256 (the above are commercial products). Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade name; Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (trade name; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN -103S, EOCN-104S, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), TTA3150 (manufactured by Kusumoto Kasei Co., Ltd.), Denacol TEPIC -L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like, but are not limited thereto.

The amount of the epoxy compound compounded is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by weight of the colorant. If it is less than 0.5 parts by mass, the effect of improving the contrast ratio and heat resistance is small.

(oxetane compound)
An oxetane compound is preferably added to the coloring composition of the present invention. As the oxetane compound, any known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those having a monofunctional oxetane group, those having a bifunctional oxetane group, and those having a bifunctional or higher oxetane group.

Examples of monofunctional oxetane groups include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3
-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3- ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane and the like.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd., and the like.

Examples of difunctional oxetane groups include 4,4′-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl) and 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]. Benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3- oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene Glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis( 3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3 -oxetanylmethyl)ether and the like.
Specific examples include OXBP, OXTP manufactured by Ube Industries, OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd., and the like.

Examples of oxetane groups having two or more functional groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa(3-ethyl). -3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3- ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl)ether, oxetane group-containing resin (eg, oxetane-modified phenolic novolac resin described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as OXE-30 described above. Such polymers can be obtained using known polymerization methods.

The content of the oxetane compound used in the coloring composition of the present invention is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on 100% by weight of the non-volatile content of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because a coating film having good water stain resistance and high chemical resistance can be obtained.

(melamine compound)
A melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Preferred in the present invention are methylol-type and ether-type melamine compounds having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. If the average number of methylol groups and/or ether groups per melamine ring is less than 5.0, the number of reaction points is small, and the crosslinked structure at the time of curing is not sufficiently dense. The effect of improvement may be small.

Commercially available products include, for example, Nicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS -001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Nippon Cytec Industries Co., Ltd.), etc., but are not limited thereto.

Among them, dicarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, and MW having an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more -22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.), etc. , is preferable in that a dense crosslinked structure can be obtained.

(curing agent)
Further, the coloring composition for color filters of the present invention may contain a curing agent (curing accelerator) and the like, if necessary, in order to assist curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and can react with thermosetting compounds. Any hardener may be used. Curing agents include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl- 4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino -S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be done. These may be used individually by 1 type, and may use 2 or more types together. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

(Photosensitive coloring composition)
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (C), a photopolymerizable monomer (D), and optionally a sensitizer (H), a thiol-based chain transfer agent, an ultraviolet absorber, Polymerization inhibitors, antioxidants and the like are added.

<Photoinitiator (C)>
The photosensitive composition of the present invention contains a photoinitiator (C). By containing a photopolymerization initiator, the composition can be cured by ultraviolet irradiation and the filter segment can be formed by photolithography. It is preferably prepared in the form of a solvent-developable or alkali-developable photosensitive composition by adding a photopolymerization initiator.

Photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 Acetophenone compounds such as -[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4' -methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 -Diisopropylthioxanthone or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6- Bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s- triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4- Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as 2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds.
These photopolymerization initiators can be used singly or as a mixture of two or more at any ratio as required.

Commercially available acetophenone compounds include "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and "IRGACURE 369" all manufactured by BASF. "(2-(dimethylamino)-2
-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl)-butan-1-one and phosphine compounds are all manufactured by BASF, "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), "IRGACURE TPO" ”(2,4,6-
trimethylbenzoyldiphenylphosphine oxide), and the like.

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

(Oxime ester compound)
In oxime ester-based compounds, absorption of ultraviolet rays causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the coloring composition is high, the UV transmittance of the coating film may be low and the degree of curing of the coating film may be low. More preferably, it is an oxime ester photopolymerization initiator represented by the general formula (20).

(Oxime ester photopolymerization initiator represented by general formula (20))
general formula (20)

In general formula (20),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group; , an alkylsulfinyl group, an arylsulfinyl 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,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group; , an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or -CO- group,
Y ³ is 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); etc. is preferable.

Examples of the optionally substituted alkenyl group for Y ¹ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, which have a plurality of carbon atoms in the structure. - may have a carbon double bond, 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, cyclopentadienyl group and the like, but are not limited thereto.

The optionally substituted alkyl group for Y ¹ includes a straight chain having 1 to 18 carbon atoms,
A branched, monocyclic or condensed polycyclic alkyl group, or a straight, branched, monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more -O- groups. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of linear or branched alkyl groups having ₂ to 18 carbon atoms and optionally interrupted by _one or _more --O-- include --CH.sub.2--O--CH.sub.3 and --CH.sub.2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —(CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 -(CH2- _CH2 - _CH2 -O) _m - _CH3 (where m is from 1 to 5), _{-CH2 -} CH( _CH3 )-O _- CH2- CH ₃ , --CH ₂ --CH--(OCH ₃ ) ₂ and the like can be mentioned, but are not limited to these.

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

The optionally substituted alkyloxy group for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or an alkyloxy group having 2 to 18 carbon atoms. Included are linear, branched, monocyclic or fused polycyclic alkyloxy groups optionally interrupted with one or more -O-. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms include methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy and hexyloxy. group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group , 4-decylcyclohexyloxy group and the like, but are not limited thereto. Specific examples of linear or branched alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more --O-- include --O--CH ₂ --O--CH ₃ , -O- _CH2 - _CH2 -O- _CH2 - _CH3 , -O- _CH2 - _CH2 - _CH2 -O- _CH2 - _CH3 , -O-( _CH2 - _CH2 -O) _n —CH ₃ (where n is 1 to 8), —O—(CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —O—CH ₂ -CH( _CH3 )-O _- CH2-
CH ₃ , --O--CH ₂ --CH--(OCH ₃ ) ₂ and the like can be mentioned, but are not limited to these.

Specific examples of monocyclic or condensed polycyclic alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

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

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

Examples of the optionally substituted heterocyclic group for Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho[2,3-b]thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl 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-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanylyl group, quinazolinyl 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, phenalsazinyl group, isothiazolyl group, phenothiazinyl group , isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group , a morpholinyl group, a thioxantryl group, a 4-quinolinyl group, a 4-isoquinolyl group, a 3-phenothiazinyl group, a 2-phenoxathinyl group, a 3-coumarinyl group and the like, but are limited thereto. not a thing

Examples of the optionally substituted heterocyclic oxy group for Y ¹ include monocyclic or condensed polycyclic heterocyclic oxy groups having 4 to 18 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. 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, and a 2-carbazolyloxy group. Ruoxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like can be mentioned, but not limited to these.

The optionally substituted alkylsulfanyl group for Y ¹ has 1 to 1 carbon atoms
8 linear, branched, monocyclic or condensed polycyclic alkylthio groups, specific examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio and decylthio , dodecylthio group, octadecylthio group and the like, but are not limited to these.

The optionally substituted arylsulfanyl group for Y ¹ has 6 to 18 carbon atoms.
A monocyclic or condensed polycyclic arylthio group, specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group, and the like. It is not limited.

The optionally substituted alkylsulfinyl group for Y ¹ has 1 to 20 carbon atoms.
is preferred, and specific examples thereof include methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, Examples include, but are not limited to, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, and the like.

The optionally substituted arylsulfinyl group for Y ¹ has 6 to 30 carbon atoms.
An arylsulfinyl group is preferred, and specific examples include a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2 -butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, Examples include, but are not limited to, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group and the like.

The optionally substituted alkylsulfonyl group for Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Examples include, but are not limited to.

The optionally substituted arylsulfonyl group for Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group , 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Examples include, but are not limited to, a phenylsulfonyl group.

The acyl group which may have a substituent in Y ¹ is a hydrogen atom or a C 1 to 18
A linear, branched, monocyclic or condensed polycyclic aliphatic bonded carbonyl group, a carbonyl group substituted with an alkyloxy group having 2 to 20 carbon atoms, a monocyclic or condensed polycyclic group having 6 to 18 carbon atoms A carbonyl group bonded to a cyclic aryl group, 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, and 4 to 18 carbon atoms carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group is bonded, specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonyl group, oleoyl group, cinnamoyl group, benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2- naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1 -naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthuryloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group and the like, but are limited to these. not something.

The acyloxy group which may have a substituent for Y ¹ includes an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group and a pentanoyloxy group. group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the optionally substituted amino group for Y ¹ include an amino group, an alkylamino group,
dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzylamino group, dibenzylamino group and the like.

Here, the alkylamino group includes methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group and dodecylamino group. , octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group and the like; , but not limited to these.

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

The arylamino group includes anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned, but not limited to these.

The diarylamino group includes, but is not limited to, diphenylamino group, ditolylamino group, N-phenyl-1-naphthylamino group, N-phenyl-2-naphthylamino group and the like.

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

The phosphinoyl group which may have a substituent in Y ¹ includes a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group and a dipropylphosphinoyl group. group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis(2,4,6-trimethylphenyl)phosphinoyl group and the like, but are limited to these. not to be

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

Examples of the optionally substituted sulfamoyl group for Y ¹ include sulfamoyl groups having 0 to 30 carbon atoms, and specific examples include sulfamoyl groups, N-alkylsulfamoyl groups and N-arylsulfamoyl groups. groups, N,N-dialkylsulfamoyl groups, N,N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamoyl groups, and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group. famoyl 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-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylamino phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,N-dimethylsulfamoyl group group, N,N-dibutylsulfamoyl group, N,N-diphenylsulfamoyl group and the like, but are not limited thereto.

an alkenyl group, an alkyl group, an alkyloxy group, which may have a substituent for Y ² ,
Aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, acyloxy groups, and amino groups include those described above. An alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an aryl group which may have a substituent, a substituent An aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic oxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, a substituent arylsulfanyl group optionally having substituent(s), alkylsulfinyl group optionally having substituent(s), arylsulfinyl group optionally having substituent(s), alkylsulfonyl group optionally having substituent(s), substituent(s) is synonymous with an arylsulfonyl group which may optionally have a substituent, an acyloxy group which may have a substituent, and an amino group which may have a substituent.

Examples of substituents on Y ¹ and Y ² include halogen groups such as fluorine, chlorine, bromine and iodine atoms, alkoxy groups such as methoxy, ethoxy and tert-butoxy, phenoxy, and p-tolyloxy. Aryloxy group such as group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group , an acyl group such as a methacryloyl group and a methoxalyl group, an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group, a phenylsulfanyl group, an arylsulfanyl group such as a p-tolylsulfanyl group, a methylamino group, a cyclohexylamino group and the like. alkylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, Alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl In addition to heterocyclic groups such as aryl groups, furyl groups, thienyl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group and the like.
One or more or more than one of these substituents may be present, and the hydrogen atoms of these substituents may be further substituted with other substituents.

Among the oxime ester photopolymerization initiators represented by the general formula (20), the oxime ester photopolymerization initiators represented by the following general formula (21) or (22) have excellent sensitivity and are more preferable. .

[Oxime ester photopolymerization initiator represented by general formula (21)]
general formula (21)

In general formula (21), Z in general formula (20) is a —CO— group and Y ³ is Ph—S—Ph—
Y ⁴ to Y ⁶ are preferably hydrogen atoms or optionally substituted alkyl or aryl groups. The optionally substituted alkyl group or optionally substituted aryl group for Y ⁴ to Y ⁶ is the same as the alkyl group or aryl group for Y ¹ and Y ² .

Furthermore, Y ¹ is an aryl group which may have a substituent, Y ² is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ⁴ and Y ⁶ are hydrogen atoms. Y ⁵ is preferably a hydrogen atom or a Y ⁷ --CO-- group, more preferably.

Y ⁷ is, for example, a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
Alkoxy groups such as methoxy, ethoxy and tert-butoxy groups, aryloxy groups such as phenoxy and p-tolyloxy groups, alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl groups, acetoxy and propionyloxy , acyloxy groups such as benzoyloxy group, acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, phenylsulfanyl group , an arylsulfanyl group such as a p-tolylsulfanyl group, a methylamino group, an alkylamino group such as a cyclohexylamino group, a dimethylamino group, a diethylamino group, a morpholino group, a dialkylamino group such as a piperidino group, a phenylamino group, p-tolylamino arylamino group, methyl group, ethyl group, tert-butyl group, alkyl group such as dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, benzofuranyl group In addition to heterocyclic groups such as aryl groups, furyl groups, thienyl groups, etc., 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, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group and the like.

More preferred substituents of Y ² are cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclooctadecyl groups.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (21) include photopolymerization initiators represented by the following chemical formulas (21-1) and (21-2).

General formula (22) corresponds to the case where Y ³ in general formula (20) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

Furthermore, an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ² or may have a substituent. A good aryl group is preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group as Y ⁷ to Y ¹⁴ .

When Z in general formula (22) is a direct bond, an oxime ester photopolymerization initiator represented by general formula (22a) below is preferred.

"Oxime ester photopolymerization initiator represented by general formula (22a)"
general formula (22a)

General formula (22a) corresponds to the case where Z in general formula ⁽ 22) is a direct bond and Y is a monovalent organic group containing a carbazole group which may have a substituent. ^Y7 ~
Y ¹⁰ and Y ¹² to Y ¹³ are hydrogen atoms.
Also, Y ¹¹ is preferably a Y ¹⁵ --CO-- group or a nitro group. Y ¹⁵ has the same meaning as the substituent for Y ¹ and Y ² and is preferably an optionally substituted aryl group. The Y ¹⁵ --CO-- group is preferably an acyl group which may further have a substituent, such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group. A benzoyl group which may have a substituent or a nitro group is more preferred. Y ¹⁴ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group.

In addition, the substituent of the benzoyl group which may have a substituent is preferably an alkyl group having 1 to 20 carbon atoms or an alkyloxy group. Further, the alkyl group is preferably a methyl group or an ethyl group. Among the alkyloxy groups, straight-chain, branched-chain, or alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 2 to 18 carbon atoms in Y ¹ optionally interrupted by one or more —O— It is synonymous with alkyloxy group.

Y ² is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms, and preferred substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, A cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and the substituent is preferably an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group. An alkoxy group such as is preferred.

Examples of the oxime ester photopolymerization initiator represented by the general formula (22a) include photopolymerization initiators represented by the following chemical formulas (22a-1) to (22a-6).

"Oxime ester photopolymerization initiator represented by general formula (22b)"
When Z in general formula (22) is a —CO— group, an oxime ester photopolymerization initiator represented by general formula (22b) below is preferred.

general formula (22b)

General formula (22b) corresponds to the case where Z in general formula (22) is a —CO— group and Y is a monovalent organic group containing a carbazole group which may have a substituent ^, and a keto type carbazole group. It is an oxime ester photopolymerization initiator having Y ⁷ to Y ¹³ are preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group, and Y ¹⁴
is preferably an aryl group which may have a substituent. 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 the general formula (22b) include photopolymerization initiators represented by the following chemical formulas (22b-1) to (22b-4).

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (IR
GACURE OXE-01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02), N- 1919 (manufactured by ADEKA), TRONLYTR-P
BG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Tenryu New Materials Co., Ltd.) and the like are commercially available. In addition, oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photopolymerization initiator.

The content of the oxime ester compound is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass based on 100 parts by mass of the colorant, from the viewpoint of photocurability and developability. If it is less than 2 parts by mass, the adhesion of the formed pattern to the base material will be poor, and if it exceeds 50 parts by mass, problems may occur in developability and brightness may decrease after heat treatment at 230°C.

<Photopolymerizable monomer (D)>
The photopolymerizable monomer (D) includes monomers or oligomers that are cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth) Acrylates, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 - hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylates, tricyclodecanyl (meth)acrylates, ester acrylates, methylolated melamine (meth)acrylates, epoxy (meth)acrylates, various acrylic and methacrylic acid esters such as urethane acrylates, (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, etc., but not necessarily limited to these not to be
These photopolymerizable compounds can be used singly or as a mixture of two or more at an arbitrary ratio as required.

These commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARADMAND, and KAY manufactured by Nippon Kayaku Co., Ltd.
ARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARAD R-604, KA
YARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA
, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPH
A-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD
DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and M-303, M-305, M-3 manufactured by Toagosei Co., Ltd.
06, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, Viscoat #335HP, Viscoat #700, Viscoat #295, Viscoat manufactured by Osaka Organic Co., Ltd. #330, Viscoat #360, Viscoat #GPT, Viscoat #400, Viscoat #405, Shin-Nakamura Chemical Co., Ltd. A-9300 and the like can be preferably used.

The amount of the photopolymerizable monomer (D) is preferably 5 to 400 parts by mass based on the total weight of the colorant (100 parts by mass), and from the viewpoint of photocurability and developability, 10 to 400 parts by mass. It is more preferably 300 parts by mass.

(Polymerizable compound having acid group)
The photopolymerizable monomer (D) in the present invention may contain a photopolymerizable monomer having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Examples of the photopolymerizable monomer having an acid group include, for example, poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohol and (meth)acrylic acid, and esters of dicarboxylic acids; Esterified products with monohydroxyalkyl (meth)acrylates and the like can be mentioned. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

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

These photopolymerizable monomers having an acid group can be used singly or as a mixture of two or more at any ratio as required.

(Polymerizable compound having urethane bond)
The photopolymerizable monomer (D) in the present invention may contain a photopolymerizable monomer containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional polyfunctional obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. urethane acrylate and the like.

(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, a reaction product of an epoxy group-containing compound and carboxy (meth) acrylate,
Examples include hydroxyl group-containing polyol polyacrylate.

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

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the resistance of the coating increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

These commercial products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., Shin-Nakamura Chemical Co., Ltd. UA-160TM, manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4108F, UV-4117F, etc. can be preferably used.

These photopolymerizable monomers having a urethane bond may be used singly or as a mixture of two or more at any ratio as required.

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

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

These sensitizers can be used singly or as a mixture of two or more at any ratio as required.
Commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F"(4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.). be done.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

The content when using a sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photoradical polymerization initiator contained in the coloring composition, from the viewpoint of photocurability and developability. It is more preferably 5 to 50 parts by mass.

<Thiol chain transfer agent>
The coloring composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using a thiol together with a photoinitiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen, so that the resulting colored composition has high sensitivity. .

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

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

These thiol-based chain transfer agents can be used singly or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0%, of the total non-volatile content of the coloring composition. Within this range, the effect of the chain transfer agent is enhanced, and the sensitivity, tapered shape, wrinkles, film shrinkage and the like are improved.

<Ultraviolet absorber>
The coloring composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. If the content of the UV absorber is less than the above, the effect of the UV absorber is small and resolution cannot be ensured. There may be a problem such as being stuck.

At this time, when the coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the coloring composition. When the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above range, the adhesion may be weakened and pixel peeling may occur.

At this time, when the coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

Examples of benzotriazole organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3-tert-butyl -4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H -benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-
3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(
3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy- 5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

More specifically, BASF "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN326"
, "TINUVIN 328", "TINUVIN 329", "TINUVIN 360
”, “TINUVIN 384-2”, “TINUVIN 900”, “TINUVIN
928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, and "RUVA-93" manufactured by Otsuka Chemical.

Triazine organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis (2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)- Reaction product of 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate, 2,4-bis "2-hydroxy-4-butoxyphenyl ”-6-(2,4-dibutoxyphenyl)-1,3-5-triazine and the like.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd., "
TINUVIN 400”, ”TINUVIN 405”, ”TINUVIN 460”,
"TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1
577ED”, “ADEKA STAB LA-46”, “ADEKA STAB LA-F70” manufactured by ADEKA, and “CYASORB UV-1164” manufactured by Sun Chemical.

Benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like.

More specifically, "KEMIISORB 10", "KEMIISOR
B 11", "KEMISORB 11S", "KEMISORB 12", "KEMIS
ORB 111”, “SEESORB 101” manufactured by Shipro Kasei Co., Ltd., “SEESORB 10
7”, and “ADEKA STAB 1413” manufactured by ADEKA.

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

Polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkylcatechol compounds such as butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, alkylresorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide Examples include oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and phloroglucine. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition from oxidizing and yellowing due to the thermal process during thermal curing and ITO annealing, and increases the transmittance of the coating film. be able to. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator will increase the yellowing of the thermal process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. , phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Moreover, the antioxidant used in the present invention preferably does not contain a halogen atom.

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

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-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4- nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2' thiodiethylbis-(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, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide) and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

Specific examples include Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO80, AO330 manufactured by ADEKA Corporation; 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

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-butane tetracarboxylate, 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}], dimethyl succinate and 1- Polycondensate with (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-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.
Specific examples include ADEKA Co., Ltd. ADEKA STAB LA-52, LA-57, LA-63
P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB29, 62, 77, 29 manufactured by Chemipro Kasei Co., Ltd., 94, Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100 manufactured by BASF Corporation, Cyasorb UV-3346, UV-3529, UV-3853 manufactured by Sun Chemical Co., Ltd., and the like.

Phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl phosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4' isopropylidenediphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2, 4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples include ADEKA Co., Ltd. ADEKA STAB PEP-36, PEP-8, and HP-1
0, Adekastab 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, and HostanoxP-EPQ manufactured by Clariant Chemicals.

Sulfur antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]- o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3- (dodecylthio)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei.

As the benzotriazole-based antioxidant, an oligomer-type or polymer-type compound having a benzotriazole structure can be used.
Specific examples include ADEKA Co., Ltd. ADEKA STAB LA-29, LA-31RG, LA-
32, LA-36, -412S, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., and TINUVIN PS, 99-2, 384-2, 900, 928, 1130 manufactured by BASF Corporation.

Benzophenone 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 the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Specific examples include Adeka Stub 1413 manufactured by ADEKA Corporation and KEMI manufactured by Chemipro Kasei Co., Ltd.
Examples include SORB10, 11, 11S, 12, 111, UV-12 and UV-329 manufactured by Sun Chemical Co., Ltd., and the like.

Triazine antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Specific examples include Adekastab LA-46 and F70 manufactured by ADEKA Corporation, KEMIISORB102 manufactured by Chemipro Kasei Corporation, TINUVIN400, 405, 460, 477 and 479 manufactured by BASF Corporation, and Cyasorb UV-1164 manufactured by Sun Chemical.

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

These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

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

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

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane , N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene ) aminosilanes such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane; , mercaptos such as 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, Examples include silane coupling agents such as isocyanates such as 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the coloring composition. Within this range, the effect is enhanced and the balance between adhesion, resolution and sensitivity is good, which is more preferable.

<Leveling agent>
A leveling agent is preferably added to the colored composition of the present invention for the purpose of improving the coating properties of the composition on a transparent substrate and the drying properties of the colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants and anionic surfactants can be used.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK- 333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray Dow Corning Co., Ltd. FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22-4272 , X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, etc. mentioned.

Fluorinated surfactants include (surfactant or leveling) agents having a fluorocarbon chain.
Specific examples include Surflon S-242, S-243, S-4 manufactured by AGC Seimi Chemical Co., Ltd.
20, S-611, S-651, S-386, DIC Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570 , F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21, Sumitomo 3M FC-4430, FC-4432, Mitsubishi Materials Electronic Chemicals EF-PP31N09 , EF-PP33G1, EF-PP32C1, Futergent 602A manufactured by Neos Co., Ltd., and the like.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ethers, polyoxyalkylene alkyl ethers, polyoxyphenylene distyrenated phenyl ethers, polyoxyethylene tribenzylphenyl ethers, polyoxyethylene polyoxypropylene glycols, polyoxyethylene alkenyl ethers, polyoxyethylene nonylphenyl ethers,
Polyoxyethylene alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan ester Oleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triiso Stearate, polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol mooleate, polyoxyethylene hydrogenated castor oils, polyoxyethylene alkylamines, alkylalkanolamides, alkylbetaines such as alkylimidazolines and alkyldimethylaminoacetic acid betaine;

Specific examples include Kao Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P, EMULGEN 350, EMULGEN 404, EMULGEN 408, EMULGEN 409PV, EMULGEN 420, EMULGEN 430, EMULGEN 705, EMULGEN 707, EMULGEN 709, EMULGEN 1108, EMULGEN 1118S-70, EMULGEN 1135S-70, EMULGEN 1150S-60, EMULGEN 2020G-HA, Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latemul PD -430, Latemul PD-430S, Latemul PD450, Rheodor SP-L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheodor SP-S30V, Rheodor SP-O10V, Rheodor SP-O30V, Rheodor Super SP -L1, Rheodol AS-10V, Rheodol AO-10V, Rheodol AO-15V, Rheodol TW-L120, Rheodol TW-L106, Rheodol TW-P120, Rheodol TW-S120V, Rheodol TW-L106V, Rheodol TW-S320V, Rheodol TW -O120V, Rheodol TW-O106V, Rheodol TW-IS399C, Rheodol Super TW-L120, Rheodol 430V, Rheodol 440V, Rheodol 460V, Rheodol MS-50, Rheodol MS-60, Rheodol MO-60, Rheodol MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60 (K), Amit 102, Amit 105, Amit 105A, Amit 302, Amit 320, Amino PK- 02S, Aminone L-02, Homogenol L-95, Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 6 manufactured by ADEKA Co., Ltd. 2, 64, 71, 72, 101, 121, Adecapluronic (registered trademark) TR-701, 702, 704, 913R and the like.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.
Specific examples include Acetamine 24 and 26 manufactured by Kao Corporation, Kotamine 24P and 86P Conc, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and (meth)acrylic acid-based (co)polymer Polyflow No. 1 manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Specific examples include Futergent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adekacol TS-230E, PS-440E, and EC-8600.

When the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0% by mass, more preferably, based on the total non-volatile content of the composition of the present invention. is 0.005 to 1.0% by mass. Within this range, the applicability of the coloring composition, the pattern adhesion, and the transmittance are well balanced.
The coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

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

When used as a coloring composition for color filters (resist material), it can be prepared as a solvent-developing or alkali-developing coloring composition. The solvent-developable or alkali-developable colored composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and additives. etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersing aid>
When the colorant is dispersed in the colorant carrier, a dispersing aid such as a pigment derivative, a dispersant, or a surfactant may be contained as appropriate. Since the dispersing aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has excellent brightness, contrast, and storage stability. becomes better. The dye derivative and dispersant are as described above.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

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

<Removal of coarse particles>
The colored dispersion or photosensitive composition of the present invention can be separated into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm, by means of centrifugation, filtration with a sintered filter or membrane filter, or the like. It is preferable to remove the above coarse particles and mixed dust. Thus, the coloring composition preferably does not substantially contain particles of 0.5 μm or larger. More preferably, it is 0.3 μm or less.

<Solid-state image sensor>
The color filter segment according to the present invention can be formed by using a known method without any particular limitation. is preferred.
An embodiment of the present invention is a method for producing a color filter, characterized by having a color filter segment obtained by curing the coloring composition described above. It contains 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 green filter segment, red filter segment and blue filter segment. Other than the colored filter segment related to the present invention, it may be formed using a known colored composition containing a color pigment, a color dye, or both a color pigment and a color dye. The method for forming the colored filter segment is not particularly limited, but it is common to use a photosensitive colored composition that is a negative resist.

When the color filter segment is formed on a predetermined corresponding photoelectric conversion element, a negative green film formed from a negative photosensitive green composition constitutes a negative color resist layer, and in this case the negative type The thickness of the color resist layer is set in the range of 0.1 μm to 3.0 μm.

On the surface of the negative color resist layer formed of the negative colored film, a plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed are pattern-exposed using a photomask.
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- to 5-fold reticle and has a pattern whose dimension is 4- to 5-fold larger than the dimension of the pattern to be exposed on the surface of the negative color resist layer. Then, a stepper exposure apparatus (not shown) is used to reduce the photomask pattern to 1/4 to 1/5 and expose the surface of the negative type color resist layer.

Following the exposure step, an alkali development treatment (development step) is performed to dissolve the uncured portion after exposure into the developer and leave the photocured portion. A patterned film composed of color filter segments can be formed by this development step.
The developing method may be a dip method, a shower method, a spray method, a paddle method, or the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like.
It is also possible to prevent uneven development by moistening the surface to be developed with water or the like before contacting the developer. As the developer, an organic alkaline developer is desirable, which does not damage the underlying circuits. The development temperature is usually 20° C. to 30° C., and the development time is 20 to 90 seconds.
Alkaline agents contained in the developer include, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4, Examples include organic alkaline compounds such as 0]-7-undecene and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate and potassium hydrogencarbonate.
As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so that the concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used. . In the case of using a developer comprising such an alkaline aqueous solution, generally after development, the excess developer is washed away by washing (rinsing) with pure water, followed by drying.
Finally, the filter segments thus formed are hardened.

In the manufacturing method of the present invention, after performing the colored layer forming step, the exposure step, and the developing step described above, if necessary, a curing step in which the formed colored pattern is cured by post-heating (post-baking) or post-exposure. may contain Post-baking is a heat treatment after development to complete curing, and is usually performed at 100°C to 270°C. When light is used, g-line, h-line, i-line, excimer laser such as KrF and ArF, electron beam, X-ray, etc. can be used. The irradiation time is preferably 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 carry out post-exposure first.
By repeating the colored layer forming step, the exposure step, and the developing step (and the curing step, if necessary) as described above for a desired number of hues, a color filter having a desired hue is produced.

<Image sensor>
A solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter for the solid-state imaging device of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. configuration.

Solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.)
and a transfer electrode made of polysilicon or the like, and a light-shielding film made of tungsten or the like having an opening only for the light-receiving portion of the photodiode on the photodiode and the transfer electrode. A device protective film made of silicon nitride or the like is formed on the film so as to cover the entire surface of the light shielding film and the photodiode light receiving part, and the color filter for a solid-state imaging device of the present invention is formed on the device protective film. be.
Further, a configuration having a condensing means (for example, a microlens or the like; the same shall apply hereinafter) above the device protective layer and below the color filter (on the side close to the substrate), or a configuration having a condensing means above the color filter, etc. may be

The organic CMOS sensor includes a thin panchromatic photosensitive organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate. It is a two-layered hybrid structure in which an inorganic material plays a role of extracting a signal to the outside, and in principle, an aperture ratio can be made 100% for incident light.
Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on the CMOS signal readout substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments.
Arrangement of the color filter segments is not particularly limited, and a known method can be used.

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples, "part" means "mass part" and "%" means "mass%". The compounding amounts in the table are parts by mass unless otherwise specified.

Each measurement method is described below.

<Average primary particle size of pigment>
The average primary particle size of the pigment was measured by a general method of directly measuring the primary particle size from a transmission electron microscope (TEM) photograph. Specifically, the short axis diameter and long axis diameter of the primary particles of each pigment were measured, and the average was used as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was taken as the average primary particle size.

The weight-average molecular weight (Mw) and number-average molecular weight of the resin, and the ammonium salt value of the resin having a cationic group in the side chain are as follows.

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

<Resin Number Average Molecular Weight (Mn)>
The number average molecular weight molecular weight (Mn) of the resin of the present invention is determined by using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, using TSK-GEL SUPER HZM-N as a column by connecting two columns, and using THF as a solvent. It is a polystyrene-equivalent number-average molecular weight measured by

<Ammonium salt value of resin having cationic group in side chain>
The ammonium salt value of a resin having a cationic group in its side chain is determined by titration with a 0.1N aqueous solution of silver nitrate using a 5% aqueous solution of potassium chromate as an indicator, and then converted to the equivalent of potassium hydroxide. , indicates the non-volatile ammonium salt value.

<Method for producing diketopyrrolopyrrole pigment>
(Brominated diketopyrrolopyrrole pigment chemical formula (1))
200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added to a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere, and heated to 100° C. with stirring to form an alcoholate solution. prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90° C. with stirring to prepare a solution of their mixture. The heated solution of this mixture was slowly added dropwise at a constant rate over 2 hours into the above alcoholate solution heated to 100° C. while being vigorously stirred. After the dropwise addition was completed, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a jacketed reaction vessel made of glass and cooled to -10°C. This cooled mixture was cooled to 75° C. while rotating a shear disk with a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser. The solution was added in small portions. At this time, the rate of adding the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always kept at -5 ° C. or less. was added in portions over approximately 120 minutes, adjusting the . After addition of the alkali metal salt, red crystals precipitated to form a red suspension. Subsequently, the resulting red suspension was washed with an ultrafiltration device at 5° C. and filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0° C. to form a suspension having a methanol concentration of about 90%, stirred at 5° C. for 3 hours, and subjected to particle sizing and washing accompanied by crystal transition. Subsequently, the water paste of the diketopyrrolopyrrole compound obtained by filtration with an ultrafilter is dried at 80° C. for 24 hours and pulverized to obtain a brominated diketopyrrolo compound represented by the chemical formula (1). 150.8 parts of pyrrole pigment are obtained.

(Diketopyrrolopyrrole pigment formula (2-1))
220 parts of tert-amyl alcohol was put into reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Then, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following formula (23) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in reaction vessel 2. It was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering and washing with methanol, diketopyrrolo represented by formula (2-1) 88.1 parts of pyrrole pigment are obtained.

(Diketopyrrolopyrrole pigment formula (2-2))
Except for changing 60.9 parts of 4-cyanobiphenyl to 54.1 parts of 4-tert-butylbenzonitrile, diketopyrrolopyrrole pigment formula (2-1) was produced in the same manner as in formula (2-2) 83.9 parts of a diketopyrrolopyrrole pigment represented by are obtained.

(Diketopyrrolopyrrole pigment formula (2-3a))
Except for changing 60.9 parts of 4-cyanobiphenyl to 68.7 parts of N-butyl-4-cyanobenzamide, the diketopyrrolopyrrole pigment formula (2-1) was produced in the same manner as the formula (2-3a). ) to obtain 87.0 parts of a diketopyrrolopyrrole pigment represented by

(Diketopyrrolopyrrole pigment formula (2-3b))
The diketopyrrolopyrrole pigment formula (2-1) was produced in the same manner as the formula (2-3b), except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide. ) to obtain 86.9 parts of a diketopyrrolopyrrole pigment.

(Diketopyrrolopyrrole pigment formula (2-4a))
Except for changing 60.9 parts of 4-cyanobiphenyl to 87.8 parts of N,N-dibutyl-4-cyanobenzamide, the diketopyrrolopyrrole pigment formula (2-1) is produced in the same manner as the formula (2 87.1 parts of the diketopyrrolopyrrole pigment represented by -4a) were obtained.

(Diketopyrrolopyrrole pigment formula (2-19))
220 parts of tert-amyl alcohol was placed in reaction vessel 1, and while cooling in a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90°C. Then, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (24) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in reaction vessel 2. It was dissolved and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering and washing with methanol, diketopyrrolopyrrole represented by formula (2-19) 87.8 parts of pigment are obtained.

<Preparation of micronized pigment>
(Production of finely divided pigment (A-1))
100 parts of the brominated diketopyrrolopyrrole pigment of formula (1), 1000 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is put into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C for a day and night, and pulverized. As a result, 96.9 parts of finely divided pigment (A-1) having a diketopyrrolopyrrole pigment was obtained. The average primary particle size was 33.1 nm.

(Production of finely divided pigment (A-2))
Manufacture of the finely divided pigment (A-1) was carried out in the same manner, except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to 100 parts of the diketopyrrolopyrrole pigment of formula (2-1). , to obtain 96.5 parts of a diketopyrrolopyrrole micronized pigment (A-2). The average primary particle size was 36.8 nm.

(Production of finely divided pigment (A-3))
In the same manner as in the production of finely divided pigment (A-1), except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the diketopyrrolopyrrole pigment of formula (2-2). 98.1 parts of ketopyrrolopyrrole micronized pigment (A-3) were obtained. The average primary particle size was 29.9 nm.

(Production of finely divided pigment (A-4))
In the same manner as in the production of finely divided pigment (A-1), except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the diketopyrrolopyrrole pigment of formula (2-3a). 98.0 parts of ketopyrrolopyrrole micronized pigment (A-4) was obtained. The average primary particle size was 30.7 nm.

(Production of finely divided pigment (A-5))
In the same manner as in the production of finely divided pigment (A-1), except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the diketopyrrolopyrrole pigment of formula (2-3b). Thus, 98.4 parts of ketopyrrolopyrrole micronized pigment (A-5) were obtained. The average primary particle size was 31.2 nm.

(Production of finely divided pigment (A-6))
In the same manner as in the production of finely divided pigment (A-1), except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the diketopyrrolopyrrole pigment of formula (2-4a). Thus, 97.5 parts of ketopyrrolopyrrole-based finely divided pigment (A-6) were obtained. The average primary particle size was 35.4 nm.

(Production of finely divided pigment (A-7))
In the same manner as in the production of finely divided pigment (A-1), except that 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) was changed to the diketopyrrolopyrrole pigment of formula (2-19). Thus, 97.5 parts of ketopyrrolopyrrole-based finely divided pigment (A-7) were obtained. The average primary particle size was 35.4 nm.

(Production of finely divided pigment (A-8))
Except for changing 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) to 90 parts of the brominated diketopyrrolopyrrole pigment of formula (1) and 10 parts of the diketopyrrolopyrrole pigment of formula (2-1) , in the same manner as the production of the finely divided pigment (A-1), and the diketopyrrolopyrrole-based finely divided pigment (A
-8) 97.2 parts were obtained. The average primary particle size was 37.1 nm.

(Production of finely divided pigment (A-9))
Except for changing 100 parts of the brominated diketopyrrolopyrrole pigment of formula (1) to 80 parts of the brominated diketopyrrolopyrrole pigment of formula (1) and 20 parts of the diketopyrrolopyrrole pigment of formula (2-1) , to obtain 96.8 parts of a diketopyrrolopyrrole micronized pigment (A-9). The average primary particle size was 36.5 nm.

(Production of finely divided pigment (A-10))
100 parts of brominated diketopyrrolopyrrole pigment of formula (1), 80 parts of brominated diketopyrrolopyrrole pigment of formula (1), 10 parts of diketopyrrolopyrrole pigment of formula (2-1), commercially available C.I. I. Pigment Red 254 ("Irgafore Red B-CF" manufactured by Ciba Specialty Chemicals) was changed to 10 parts in the same manner as in the production of finely divided pigment 1 (A-1), and a diketopyrrolopyrrole-based finely divided pigment was prepared. (A-10) 96.7 parts were obtained. The average primary particle size was 33.2 nm.

(Production of micronized pigment (A-11))
The brominated diketopyrrolopyrrole pigments of formula (1) are prepared from commercially available C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) was used in the same manner as in the production of the micronized pigment (A-1), and the diketopyrrolopyrrole-based micronized pigment (A- 11) Obtained 97.3 parts. The average primary particle size was 34.2 nm.

(Production of micronized pigment (A-12))
C. I. 100 parts of Pigment Red 242 ("Novopalm Scarlet 4RF" manufactured by Clariant), 1600 parts of sodium chloride and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day and night to obtain a finely divided pigment (A-12). The average primary particle size was 35.2 nm.

(Production of finely divided pigment (A-13))
anthraquinone red pigment C.I. I. Pigment Red 177 ("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals): 500 parts, sodium chloride: 500
and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120° C. for 8 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided pigment (A-13). The average primary particle size was 34.5 nm.

(Production of micronized pigment (A-14))
quinophthalone-based yellow pigment C.I. I. 100 parts of Pigment Yellow 138 (“Pariotol Yellow K0961HD” manufactured by BASF), 800 parts of pulverized salt, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 4 hours. This mixture is poured into 3000 parts of hot water, heated to about 80°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated at 80°C for 24 hours. After drying, 98 parts of finely divided pigment (A-14) were obtained. The average primary particle size was 34.3 nm.

(Production of finely divided pigment (A-15))
isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 ("Irgafor Yellow 2R-CF" manufactured by Ciba Specialty Chemicals), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 60 ° C. Kneaded for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (A-15). The average primary particle size was 34.6 nm.

(Production of finely divided pigment (A-16))
Metal complex yellow pigment (CI pigment yellow 150, Lanxess "Yellow Pigment E4GN") 100 parts, sodium chloride 1600 parts, and diethylene glycol 190 parts are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 60°C for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (A-16). The average primary particle size was 36.6 nm.

(Production of finely divided pigment (A-17))
yellow pigment C.I. I. Pigment Yellow 185 ("" manufactured by Ciba Japan) ("Pariotol Yellow D1155" manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) It was prepared and kneaded at 120° C. for 8 hours. Next, this kneaded product is put into 5 liters of hot water and stirred for 1 hour while heating to 70°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , 490 parts of finely divided pigment (A-17) were obtained. The average primary particle size was 35.9 nm.

<Production of finely divided pigments (A-18 to 20)>
The following quinophthalone compounds (a) to (c) were obtained according to the synthesis method described in JP-A-2012-226110.

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60° C. for 6 hours, and subjected to salt milling. The resulting kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , to obtain 98 parts of finely divided pigment (A-18). The average primary particle size was 31.3 nm.

100 parts of the quinophthalone compound (b), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 98 parts of finely divided pigment (A-19) were obtained. The average primary particle size was 31.1 nm.

100 parts of the quinophthalone compound (c), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 8 hours. Next, this kneaded product is put into hot water and stirred for 1 hour while heating to about 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. 97 parts of finely divided pigment (A-20) were obtained. The average primary particle size was 34.1 nm.

<Method for producing dye>
(Resin 1 having a cationic group in the side chain)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the non-volatile matter and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, reacted at 50° C. for 2 hours, heated to 80° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 01 (AR52-JK))
The C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced.
To 2000 parts of water was added 30 parts of Resin 1 having a cationic group on its side chain in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. Dye 01 (AR52), which is a salt forming compound of Acid Red 52 and Resin 1 having a cationic group in
-JK) was obtained. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.

(Dye 02 (AR289-JK))
The C.I. I. Dye 02 (AR289-JK), which is a salt-forming compound consisting of Acid Red 289 and Resin 1 having a cationic group in the side chain, was produced.
To 2000 parts of water was added 30 parts of Resin 1 having a cationic group on its side chain in terms of non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 289, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer. I. Dye 02 (AR
289-JK) was obtained. At this time, C.I. I. The content of the active coloring component derived from Acid Red 289 was 27% by mass.

(Dyes 03-04 (AR289-SA, AR289-DSA))
Dyes 03 to 04 (AR289-SA, AR289-DSA), which are the following xanthene-based sulfonic acid amide compounds, were obtained based on the description in JP-A-2013-203956.

Incidentally, Ra of the above dyes 03 and 04 has the following partial structure.

(Dyes 05-06 (DP-1, DP-2))
Exemplary Compound I-1 and Exemplary Compound III-45 were obtained according to the synthetic scheme described in Japanese Patent No. 5085256, and designated as Dyes 05 to 06 (DP-1, DP-2), respectively.

(Dye 07 (BB7-NT))
2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight: 334) is dissolved in a 7-15 mol % sodium hydroxide solution and sufficiently mixed and stirred to obtain a sodium salt thereof. After heating this 2,8-diamino-1-naphthol-5,7-disulfonic acid sodium salt aqueous solution to 70 to 90° C., Victoria Pure Blue dye (CI Basic Blue 7) is gradually added dropwise. . Also, the Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After dropping the Victoria Pure Blue dye, the mixture is stirred at 70 to 90° C. for 40 to 60 minutes for a sufficient reaction. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it can be determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration is performed and the mixture is washed with water. After washing with water, water is removed from the salt-forming compound remaining on the filter paper with a dryer and dried to form a salt of Victoria Pure Blue dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid. A compound, Dye 07 (BB7-NT), which is a triarylmethane-based salt-forming compound, was obtained.

(Dye 08 (BV10-MA))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 5.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1-(3-dimethylaminopropyl)-3-ethyl 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water, dried under reduced pressure, and purified with a silica gel column to obtain Dye 08 (BV10-MA). Yield was 51.6%.

(Dyes 09-12)
The dyes of Table 2 were used without processing.

<Method for producing dye solution>
(Dye solution (DS-01))
After the following mixture was uniformly stirred and mixed, the mixture was filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (DS-01).
Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

Dye solutions (DS-02 to 12) were obtained in the same manner as the dye solution (DS-01) except that the dye was changed to the composition shown in Table 2.

<Pigment derivative>
The following pigment derivatives were used.

Pigment derivative (1)

Pigment derivative (2)

(Resin type dispersant (1) liquid: acidic)
45.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid and 40.0 parts of ethyl acrylate were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel is heated to 80° C., and 1.0 part of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile are dissolved in 45.3 parts of cyclohexanone. solution was added and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. At this time, the number average molecular weight was 9,500. Next, add 8.0 parts of Rikashid BT-100 (manufactured by Shin Nippon Rika), 69.2 parts of cyclohexanone, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst. and reacted at 120° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. If necessary, part of the solvent is removed by distillation under reduced pressure, then propylene glycol monomethyl ether acetate is added to adjust the nonvolatile content to 50%, and a comb-shaped resin type dispersant (1) liquid having a number average molecular weight of 25,000 is obtained. got

(Resin type dispersant (2) liquid: basic)
500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate were introduced into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 90° C., and after adding 0.50 parts of AIBN, the reaction was carried out for 7 hours. After confirming that 95% of the nonvolatile matter had reacted, the solution was cooled to room temperature to obtain a 50% nonvolatile matter solution of a vinyl polymer having a weight average molecular weight of 5,200 and two free hydroxyl groups at one terminal region. Then, 90.4 parts of isophorone diisocyanate, 45.1 parts of propylene glycol monomethyl ether acetate, and 0.11 part of dibutyltin dilaurate as a catalyst were charged, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C., reacted for 3 hours, and then cooled to 40° C. to obtain a prepolymer solution having isocyanate groups. 22.2 parts of methyliminobispropylamine, 13.2 parts of dibutylamine, and 304.6 parts of propylene glycol monomethyl ether acetate were charged into a reactor 2 equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and heated to 100°C. . The prepolymer solution was added dropwise thereto over a period of 30 minutes, and the reaction was continued for 1 hour, followed by cooling to room temperature to terminate the reaction. If necessary, part of the solvent was removed by distillation under reduced pressure, and then propylene glycol monomethyl ether acetate was added to adjust the nonvolatile content to 50% to obtain a resin type dispersant (2) liquid having a number average molecular weight of 14,000. .

<Production example of binder resin (B)>
(Preparation of binder resin (B-1) liquid)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 37.2 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.) , 2,2'-azobisisobutyronitrile 1.1 parts was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more 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 nonvolatile content. A binder resin (B-1) liquid was prepared by adding acetate. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (B-2) liquid)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare a binder resin (B-2). The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (B-3) liquid)
A separable 4-necked flask equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, parachlorate was added from the dropping tube. Milphenol ethylene oxide-modified acrylate (Toagosei Aronix M110) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of the glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours until the acid value of the non-volatile matter reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (B-3) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

(Preparation of binder resin (B-4) liquid)
A separable flask equipped with a cooling pipe was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (“PERBUTYL O” manufactured by NOF Corporation), and 40 parts of propylene glycol monomethyl ether acetate were thoroughly stirred and mixed, and A chain transfer agent dropping tank was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate. A reactor was charged with 395 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90°C. After the temperature of the reactor was stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition was performed over 1,35 minutes while maintaining the temperature at 90°C. After 60 minutes from the end of the dropwise addition, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (volume ratio) was started. Then, 70 parts of glycidyl methacrylate and 0.2 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol) were added to the reactor. 4 parts of triethylamine and 0.8 parts of triethylamine were added and reacted at 110° C. for 12 hours. Then, 150 parts of propylene glycol monomethyl ether acetate is added and cooled to room temperature, and about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. A binder resin (B-4) liquid was obtained by adding propylene glycol monomethyl ether acetate to 20% by mass. The resin had a weight average molecular weight of 18,000 and an acid value of 2 mgKOH/g per nonvolatile matter.

<Method for producing pigment dispersion>
[Production Example 1]
(Preparation of pigment dispersion (R-1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), the pore size is 5.5 mm. A pigment dispersion (R-1) having a non-volatile content of 24.7% by mass was prepared by filtration through a 0 μm filter.
Pigment (A-1): 20.0 parts Pigment derivative (1): 0.5 parts Resin type dispersant ((1): 50% non-volatile liquid): 2.0 parts Binder resin (B-1: non-volatile 20% liquid): 16.0 parts Solvent (P): 61.5 parts

[Production Examples 2 to 20]
(Preparation of pigment dispersion (R-2 to 20))
Pigment dispersions (R-2 to R-20) were prepared in the same manner as in Production Example 1, except that the material types and weights were changed as shown in Table 3.

<Method for producing colored composition>
[Production Example 21]
(Preparation of colored composition (X-1))
The following raw materials are mixed, stirred and filtered through a filter with a pore size of 1.0 μm to give a colored composition (X-1)
got
Pigment dispersion A1 (R-1: non-volatile content 24.7% liquid): 51 parts Pigment dispersion A2 (R-14: non-volatile content 24.7% liquid): 5 parts Binder resin (B-1: non-volatile content 20 % liquid): 31 parts Solvent (P): 13 parts

[Production Examples 22 to 56]
(Preparation of colored composition (X-2 to 36))
A coloring composition (X-2 to 36) was prepared in the same manner as in Production Example 1, except that the material species and mass were changed as described in Table 4.

<Method for producing a photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y
-1) was obtained.
Coloring composition (X-1: non-volatile content 20%): 50.0 parts binder resin (B-2: non-volatile content 20%): 15.0 parts photoinitiator (C): 1.8 parts photopolymerizable Monomer (D): 3.0 parts Thermosetting compound (E-1): 1.0 parts Thermosetting compound (E-2): 1.0 parts Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 parts Ultraviolet absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M : Non-volatile content 3%): 1.0 parts Storage stabilizer (N): 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 26.0 parts

[Examples 2 to 36, Comparative Examples 1 and 2]
(Preparation of photosensitive coloring composition (Y-2 to 38))
Photosensitive coloring compositions (Y-2 to 38) were prepared in the same manner as in Example 1 except that the types of the coloring composition and binder resin solution of Example 1 were changed as shown in Table 5. In addition, about each raw material, it is as follows.

<Thermosetting compound (E)>
・ Epoxy compound (E-1)
(E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel Corporation)],
(E-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(E-1-3) Equal amounts of triglycidyl isocyanurate (E-1-1) to (E-1-3) were mixed to prepare an epoxy compound (E-1).
- Oxetane compound (E-2):
3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Photopolymerizable monomer (D)>
(D-1) trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(D-2) Trimethylolpropane EO-modified triacrylate
[Aronix M350 (manufactured by Toagosei Co., Ltd.)]
(D-3) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(D-4) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(D-5) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(D-6) Polyfunctional urethane acrylate according to the following Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged in a 1-liter, 5-necked reaction vessel, reacted at 60 ° C. for 8 hours, and (meth) acryloyl group In the product, the proportion of the polyfunctional urethane acrylate (D-6) is 70% by mass, and the remainder is other photopolymerizable It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(D-7) Bifunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-8) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
The above (D-1) to (D-8) were mixed in equal amounts to obtain a photopolymerizable monomer (D).

<Photoinitiator (C)>
(C-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(C-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(C-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (manufactured by Ciba Japan)]
(C-4) 2,2′-bis(o-chlorophenyl)-4,5,4′,5′-tetraphenyl-1,2′-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(C-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(C-6) ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(C-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(C-8) bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
The above (C-1) to (C-8) were mixed in equal amounts to obtain a photopolymerization initiator (C).

<Sensitizer (H)>
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4′-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
The above (H-1) and (H-2) were mixed in equal amounts to obtain a sensitizer (H).

<Thiol chain transfer agent (I)>
(I-1) trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (I-1) to (I-5) were mixed in equal amounts to obtain a thiol-based chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) tert-butylhydroquinone and above, (J-1) to (J-3) are mixed in equal amounts, and a polymerization inhibitor is added. (J).

<Ultraviolet absorber (K)>
(K-1) 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol
[TINUVIN326 (manufactured by BASF Japan)]
(K-2) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-3) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (K-1), (K-2) and (K-3) were mixed in equal amounts to obtain an ultraviolet absorber (K).

<Antioxidant (L)>
(L-1) pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) 3,3′-dioctadecyl thiodipropanoate (L-3) tris[2 ,4-di-(tert)-butylphenyl]phosphine (L-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-octylphenyl salicylate, (L -1) to (L-5) were mixed in equal amounts to obtain an antioxidant (L).

<Leveling agent (M)>
"BYK-330" manufactured by BYK-Chemie Co., Ltd. 1 part,
DIC's "Megafac F-551" 1 copy,
A mixed solution prepared by dissolving 1 part of "EMULGEN 103" manufactured by Kao Corporation in 97 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer (N)>
(N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine (“TPP” manufactured by Hokko Chemical Industry Co., Ltd.)
The above (N-1) and (N-2) were mixed in equal amounts to obtain a storage stabilizer (N).

<Silane coupling agent (O)>
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (O-1) to (O-4) were mixed in equal amounts to obtain a silane coupling agent (O).

<Solvent (P)>
(P-1) 30 parts of propylene glycol monomethyl ether acetate (P-2) 30 parts of cyclohexanone (P-3) 10 parts of ethyl 3-ethoxypropionate (P-4) 10 parts of propylene glycol monomethyl ether (P-5) cyclo Hexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above parts by mass to obtain a solvent (P).

<Evaluation of photosensitive coloring composition>
Coating film foreign matter and heat resistance tests were carried out by the following methods. The results of the tests are shown in Table 6.

<Paint Foreign Matter Test>
Evaluation was carried out by preparing test substrates and counting the number of particles. The coloring composition was coated on a transparent substrate so that the dried coating film had a thickness of about 2.0 μm, and heated in an oven at 110° C. for 20 minutes to obtain a test substrate. For the evaluation, the surface was observed using a metallurgical microscope "BX60" manufactured by Olympus System Co., Ltd.). Magnification is 500 times, and the number of particles observable in any 5 fields of view in transmission is counted. In the following evaluation results, ◯ is good, Δ is a level that does not pose a problem in use although there are many foreign substances, and × is coating unevenness (mottling) due to foreign substances.
◯: less than 20 Δ: 20 or more and less than 100 ×: 100 or more and below Table 6 shows the results.

<Paint film heat resistance test>
A resist material is coated on a transparent substrate so that the dry coating film is about 2.5 μm, and after UV exposure is performed through a mask with a predetermined pattern, an alkaline developer is sprayed to remove uncured areas. to form the desired pattern. After that, the film was heated in an oven at 230° C. for 20 minutes and allowed to cool, and then the obtained coating film was observed under a microscope to confirm the presence or absence of crystal foreign matter.
◯: No precipitation of crystal foreign matter is observed.
x: A crystal foreign matter precipitated.
The results are shown in Table 6 below.

(Production of color filter)
Red, green, and blue color filters were formed on the device forming surface side of a silicon wafer (solid-state imaging device substrate) using the following color resists.

(Preparation of red resist material (RR-1))
The above photosensitive coloring composition (Y-1) was used as a red resist material (RR-1).

(Preparation of green resist material (RG-1))
After stirring and mixing the mixture of the following composition uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours in an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5 A green pigment dispersion 1 was prepared by filtering through a .0 μm filter.
Green pigment (C.I. Pigment Green 58) 8.4 parts Yellow pigment (C.I. Pigment Yellow 150) 3.6 parts Binder resin solution (B-1: 20%) 35.0 parts Resin type dispersant solution ("EFKA4300" manufactured by BASF) 5.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

Subsequently, a mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a green resist material (RG-1).
Green pigment dispersion 1 50.0 parts Binder resin solution (B-2: 20%) 7.5 parts Photopolymerizable monomer 2.0 parts (manufactured by Toagosei Co., Ltd. "Aronix M-402")
Dipentaerythritol hexaacrylate photopolymerization initiator (manufactured by BASF "OXE-02") 1.5 parts Cyclohexanone 39.0 parts

(Preparation of blue resist material (RB-1))
After stirring and mixing the mixture of the following composition uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours in an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5 A blue pigment dispersion 1 was prepared by filtering through a filter of .0 μm.
Blue pigment (C.I. Pigment Blue 15:6) 9.6 parts Purple pigment (C.I. Pigment Violet 23) 2.4 parts Binder resin solution (B-1: 20%) 35.0 parts Resin type dispersion Agent solution ("EFKA4300" manufactured by BASF) 5.0 parts Propylene glycol monomethyl ether acetate 48.0 parts

Subsequently, a mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a blue resist material (RB-1).
Blue pigment dispersion 1 50.0 parts Binder resin solution (B-2: 20%) 7.5 parts Photopolymerizable monomer 2.0 parts (manufactured by Toagosei Co., Ltd. "Aronix M-402")
Dipentaerythritol hexaacrylate photopolymerization initiator (manufactured by BASF "OXE-02") 1.5 parts Cyclohexanone 39.0 parts

(Production of color filter)
A red resist material (RR-1) was applied by a spin coater to the device-forming side of an 8-inch device-formed silicon wafer (solid-state imaging element substrate) substrate which had been previously sprayed with hexamethyldisilazane to form a colored film. Then, heat treatment (pre-baking) was performed using a hot plate at 100° C. for 180 seconds.
Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), pattern exposure was performed at a wavelength of 365 nm at an exposure amount of 150 mJ/cm ² through a photomask for forming 1.0 μm square red pixels. gone.
Next, after removing unexposed portions by spray development with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution, the substrate is washed with deionized water and heated at 230° C. for 12 minutes to form a red filter segment. formed. Here, the red filter segment was made to match the chromaticity of x=0.640, y=0.330 in C light source (hereinafter also used for green and blue) after heat treatment at 230.degree. In a similar manner, the green filter segment uses a green resist material (RG-1) to match the chromaticity of x = 0.290 and y = 0.600, and the blue filter segment uses a blue resist material. (RB-1) was used to match the chromaticity of x=0.150 and y=0.060, and each filter segment was formed to obtain a color filter for an image sensor.

Claims (5)

Colorant (A), binder resin (B), photopolymerization initiator (C), and photopolymerizable monomer (D),
The coloring agent (A) contains a diketopyrrolopyrrole pigment (A1) represented by the following chemical formula (1) and one or more organic pigments (A2),
The pigment (A1) is 20% by mass to 95% by mass with respect to the total amount of the colorant (A),
A photosensitive coloring composition for use in color filters for solid-state imaging devices, wherein the photopolymerizable monomer (D) contains an oxime ester initiator.

The organic pigment (A2) is C.I. I. Pigment Red 254, C.I. I. Pigment Red 242, C.I. I. Pigment Red 177, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 185, and a photosensitive coloring composition for use in a color filter for a solid-state imaging device according to claim 1, comprising one or more selected from the group consisting of yellow pigments represented by the following general formula (3): thing.
General formula (3)

[In general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or a substituent an aryl group that may have, —SO ₃ H, —COOH, and monovalent to trivalent metal salts, alkylammonium salts, phthalimidomethyl groups that may have substituents, or substituents of these acidic groups; represents a sulfamoyl group which may have,
Adjacent groups of Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may combine to form an aromatic ring which may have a substituent. ] 3. The photosensitive coloring composition for use in a color filter for a solid-state imaging device according to claim 1, further comprising a pigment derivative. A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition used in the color filter for a solid-state imaging device according to any one of claims 1 to 3. A solid-state imaging device comprising the color filter according to claim 4 .