JP2023057917A - Diketopyrrolopyrrole pigment, coloring composition, color filter and sensor - Google Patents

Abstract

To provide a diketopyrrolopyrrole pigment that achieves high coloring ability and high transmittance as a red colorant, as well as excellent dispersion stability, and to provide a pigment composition, a coloring composition, a color filter, and a sensor using the pigment.SOLUTION: The problem described above can be achieved by diketopyrrolopyrrole pigment represented by the following general formula (1).SELECTED DRAWING: None

Description

The present invention relates to diketopyrrolopyrrole pigments, coloring compositions, color filters and sensors.

In recent years, with the spread of digital cameras and camera-equipped mobile phones, the demand for image sensors such as C-MOS (Complementary Metal Oxide Semiconductor) and CCD (Charge Coupled Device) has grown significantly. ing. These image sensors generally perform color separation by arranging color filters each having filter segments of additive primary colors of B (blue), G (green), and R (red) on the light receiving elements. is.

Color filters for image sensors are required to have thinner films, improved color resolution, and improved color reproducibility. Needed. In particular, in order to increase the coloring of the coloring composition, the concentration of the coloring agent is increased, the coloring agent having a high coloring power is used, and the like.

Conventionally, C.I. I. Pigment Red 254 has been used, but its tinting strength is not sufficient to meet the recent strong demand for thinner films. Also, C.I. I. The use of Pigment Red 272 has been studied, but there are problems such as poor stability of the dispersion when the concentration is increased and low transmittance at 600 nm or more.

JP 2016-065115 A WO2020/040043

An object of the present invention is to provide a diketopyrrolopyrrole pigment which, as a red colorant, has both high tinting strength and high transmittance and excellent dispersion stability. Another object of the present invention is to provide a pigment composition, a coloring composition, a color filter, and a sensor using the pigment.

As a result of extensive research, the present inventors have achieved both high tinting strength and high transmittance by using a specific diketopyrrolopyrrole pigment as a red colorant, and have excellent dispersion stability. The discovery led to the present invention.

That is, the present invention relates to a diketopyrrolopyrrole pigment characterized by being represented by the following general formula (1).

〔一般式（１）において、Ｘ^１、Ｘ^２は、それぞれ独立して、フッ素、塩素または臭素原子を表し、Ｒ^１、Ｒ^２は、それぞれ独立して、置換基を有してもよい炭素数１～１０のアルキル基を表す。ｎ^１、ｍ^１はそれぞれ独立して１～４の整数、ｎ^２、ｍ^２はそれぞれ独立して０～５の整数を表し、ｎ^１＋ｍ^１およびｎ^２＋ｍ^２は５以下の整数である。〕 General formula (1)

[In the general formula (1), X ¹ and X ² each independently represent a fluorine, chlorine or bromine atom; R ¹ and R ² each independently represent a carbon atom optionally having a substituent represents an alkyl group of numbers 1 to 10; n ¹ and m ¹ each independently represent an integer of 1 to 4, n ² and m ² each independently represent an integer of 0 to 5, and n ¹ +m ¹ and n ² +m ² are integers of 5 or less . ]

The present invention also relates to a diketopyrrolopyrrole pigment characterized by being represented by the following general formula (2).

〔一般式（２）において、Ｙ^１～Ｙ^３は、それぞれ独立して、水素原子、Ｘ^１またはＲ^１を表し、Ｙ^４～Ｙ^６は、それぞれ独立して、水素原子、Ｘ^２またはＲ^２を表す。Ｘ^１およびＸ^２は、それぞれ独立して、フッ素、塩素または臭素原子であり、Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有してもよい炭素数１～１０のアルキル基である。ただし、Ｙ^１～Ｙ^３のうち、少なくとも一つはＸ^１であり、かつ、少なくとも一つはＲ^１である。〕 general formula (2)

[In general formula (2), Y ¹ to Y ³ each independently represent a hydrogen atom, X ¹ or R ¹ ; Y ⁴ to Y ⁶ each independently represent a hydrogen atom, X ² or R ² . X ¹ and X ² are each independently a fluorine, chlorine or bromine atom; R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms; be. However, at least one of Y ¹ to Y ³ is X ¹ and at least one is R ¹ . ]

The present invention also relates to a pigment composition comprising the diketopyrrolopyrrole pigment and a dye derivative.

The present invention also relates to a coloring composition comprising the diketopyrrolopyrrole pigment or the pigment composition, and an organic solvent.

The present invention also relates to the coloring composition, characterized by further comprising a photopolymerizable monomer and/or a photopolymerizable initiator.

The present invention also relates to the coloring composition, wherein the water content in the coloring composition is 0.1 to 2.0% by mass with respect to the entire coloring composition.

Further, in the present invention, the coloring composition contains a metal component containing a metal atom selected from Li, Na, K, Cs, Mg, Ca, Fe, Cr, and Zr, and the coloring composition as a whole contains the above The coloring composition is characterized in that the total amount of the metal atoms in the metal component is 1 to 1000 mass ppm.

The present invention also relates to a color filter having a coating formed from the coloring composition on a substrate.

The present invention also relates to a sensor having the color filter.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a diketopyrrolopyrrole pigment having both high tinting strength and high transmittance and excellent dispersion stability. Also, a coloring composition, a color filter, and a sensor using the pigment can be provided.

Each constituent component of the present invention will be described below.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented. Moreover, "C.I." mentioned in this specification means a color index (C.I.).

(diketopyrrolopyrrole pigment)
The present invention is a diketopyrrolopyrrole pigment represented by the following general formula (1).

〔一般式（１）において、Ｘ^１、Ｘ^２は、それぞれ独立して、フッ素、塩素または臭素原子を表し、Ｒ^１、Ｒ^２は、それぞれ独立して、置換基を有してもよい炭素数１～１０のアルキル基を表す。ｎ^１、ｍ^１はそれぞれ独立して１～４の整数、ｎ^２、ｍ^２はそれぞれ独立して０～５の整数を表し、ｎ^１＋ｍ^１およびｎ^２＋ｍ^２は５以下の整数である。〕 General formula (1)

[In the general formula (1), X ¹ and X ² each independently represent a fluorine, chlorine or bromine atom; R ¹ and R ² each independently represent a carbon atom optionally having a substituent represents an alkyl group of numbers 1 to 10; n ¹ and m ¹ each independently represent an integer of 1 to 4, n ² and m ² each independently represent an integer of 0 to 5, and n ¹ +m ¹ and n ² +m ² are integers of 5 or less . ]

The "alkyl group" of the alkyl group having 1 to 10 carbon atoms which may have a substituent may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, heptyl group, octyl group, decyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group etc. From the viewpoint of coloring strength and dispersion stability, it preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. "Alkyl group having a substituent" includes, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoro propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group and the like, but these include It is not limited.

In X ¹ and X ² , fluorine, chlorine or bromine all exhibit excellent tinting strength, transmittance and dispersion stability. Among them, fluorine or chlorine is preferred, and fluorine is more preferred.

From the viewpoint of coloring power and dispersion stability, the diketopyrrolopyrrole pigment in the present invention preferably has general formula (2), particularly preferably general formula (3).

〔一般式（２）において、Ｙ^１～Ｙ^３は、それぞれ独立して、水素原子、Ｘ^１またはＲ^１を表し、Ｙ^４～Ｙ^６は、それぞれ独立して、水素原子、Ｘ^２またはＲ^２を表す。Ｘ^１およびＸ^２は、それぞれ独立して、フッ素、塩素または臭素原子であり、Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有してもよい炭素数１～１０のアルキル基である。ただし、Ｙ^１～Ｙ^３のうち、少なくとも一つはＸ^１であり、かつ、少なくとも一つはＲ^１である。〕 general formula (2)

[In general formula (2), Y ¹ to Y ³ each independently represent a hydrogen atom, X ¹ or R ¹ ; Y ⁴ to Y ⁶ each independently represent a hydrogen atom, X ² or R ² . X ¹ and X ² are each independently a fluorine, chlorine or bromine atom; R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms; be. However, at least one of Y ¹ to Y ³ is X ¹ and at least one is R ¹ . ]

〔一般式（３）において、Ｘ^１、Ｘ^２は、それぞれ独立して、フッ素、塩素または臭素原子を表し、Ｒ^１、Ｒ^２は、それぞれ独立して、置換基を有してもよい炭素数１～１０のアルキル基を表す。〕 General formula (3)

[In the general formula ( ^{3 )} , X ¹ and X ² each independently represent a fluorine, chlorine or bromine atom; represents an alkyl group of numbers 1 to 10; ]

Specific examples of the diketopyrrolopyrrole pigments of the present invention are listed below, but are not limited thereto.

general formula (4)

From the viewpoint of coloring strength, transmittance and dispersion stability, among the above structures, diketopyrrolopyrrole pigments (1-4 to 9, 13 to 15, 18, 19, 21 to 23, 26, 27) are preferred, (1-4 to 6, 22, 23) and the like are particularly preferred.

<Method for producing diketopyrrolopyrrole pigment>
Although the method for producing the diketopyrrolopyrrole pigment of the present invention is not particularly limited, a diketopyrrolopyrrole pigment in which substituents are symmetrically introduced such as the diketopyrrolopyrrole pigments (1-1 to 25) can be produced most conveniently by the succinic acid diester synthesis method. That is, 2 mol of a benzonitrile compound represented by the following general formula (5) is added to 1 mol of a succinic acid diester in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or an alkali metal alkoxide. , a condensation reaction is performed at a high temperature of 80 to 110° C. to produce an alkali metal salt of the diketopyrrolopyrrole compound, and then water, alcohol, acid, etc. are added to the alkali metal salt of the diketopyrrolopyrrole compound. Various diketopyrrolopyrrole pigments can be obtained by protonating with 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.

〔一般式（５）において、Ｘ^３は、フッ素、塩素または臭素原子を表し、Ｒ^３は、置換基を有してもよい炭素数１～１０のアルキル基を表す。ｎ^３、ｍ^３はそれぞれ独立して１～４の整数を表し、ｎ^３＋ｍ^３は２～５の整数である。〕 general formula (5)

[In the general formula (5), X ³ represents a fluorine, chlorine or bromine atom, and R ³ represents an optionally substituted alkyl group having 1 to 10 carbon atoms. n ³ and m ³ each independently represent an integer of 1-4, and n ³ +m ³ is an integer of 2-5. ]

Diketopyrrolopyrrole pigments into which substituents are asymmetrically introduced, such as diketopyrrolopyrrole pigments (1-26, 27), are described in, for example, Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565. The manufacturing method is not limited to this method.

(Pigment composition)
Next, the pigment composition of the present invention will be explained. The pigment composition of the present invention contains the diketopyrrolopyrrole pigment and dye derivative of the present invention.

<Dye derivative>
A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

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

As the dye derivative contained in the pigment composition of the present invention, those derived from diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinophthalone-based pigments, and azo-based pigments as organic dye residues have coloring power, refining efficiency, and dispersion. It is preferable from the viewpoint of stability.

The dye derivative contained in the pigment composition of the present invention is preferably added in an amount of 0 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the diketopyrrolopyrrole pigment.

These dye derivatives can be used singly or in combination of two or more.

The pigment composition of the present invention may be prepared by simply mixing a diketopyrrolopyrrole pigment powder and a pigment derivative powder, but may be prepared by mixing a dissolver, high speed mixer, homomixer, kneader, roll mill, attritor, sand mill, A method of mechanically mixing pigment powder and pigment derivative powder using various grinders, a method of adding a solution containing a pigment derivative to a water or organic solvent suspension system of the pigment, and depositing the pigment derivative on the surface of the pigment. Alternatively, the pigment composition may be obtained by co-dissolving the organic pigment and the dye derivative in a solvent having a strong dissolving power such as sulfuric acid, followed by co-precipitation with a poor solvent such as water.

<Refinement of pigment>
The diketopyrrolopyrrole pigment used in the pigment composition of the present invention is preferably finely divided. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation method can be used. etc., and can be miniaturized.

The salt milling process is performed by subjecting a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent to a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like in a batch or continuous manner. In this treatment, the mixture is mechanically kneaded while being heated using a kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, most preferably 300 to 1,000 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 the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The 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, per 100 parts by mass of the pigment.

In the salt milling process, a pigment derivative may be added to improve the kneading efficiency, which is very effective for refining and regulating the particles of the pigment. The amount of the pigment derivative to be used is preferably in the range of not affecting the color tone, that is, in the range of 0.5 to 40% by weight with respect to 100% 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.

By salt milling the diketopyrrolopyrrole pigment, it can be made more uniformly fine, and the coloring power, transmittance, and stability of the dispersion can be improved in a well-balanced manner.

The average primary particle size of the diketopyrrolopyrrole pigment of the present invention is preferably in the range of 30 to 200 nm. If the average primary particle size is 200 nm or more, the coloring power is high, but the transmittance is low. If the average primary particle size is less than 30 nm, the transmittance is improved, but the resistance is lowered. In addition, when the specific surface area of the coloring agent increases, the cohesive force increases, and the dispersibility and storage stability of the coloring composition deteriorate.

The average primary particle size was measured using a transmission electron microscope (TEM) H-7650 manufactured by Hitachi High-Technologies Co., Ltd. by directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating a cube with the obtained particle size, and the volume average particle size was taken as the average primary particle size.

(Coloring composition)
The diketopyrrolopyrrole pigment or pigment composition of the present invention can be used as a coloring composition by using it in combination with an organic solvent. A binder resin, a resin-type dispersant, and other colorants may be included as necessary.

By performing dispersion treatment such as wet dispersion using two rolls, three rolls, or beads on the above raw materials, for example, the pigment derivative is adsorbed on the surface of the pigment, and the surface of the pigment becomes polar, and the resin-type dispersant is adsorbed. The compatibility with pigments, dye derivatives, resin type dispersants, organic solvents, and other additives is improved, and the dispersion stability and viscosity stability over time of the colored composition are improved. Further, by improving the compatibility, the coating film has excellent temporal stability when the coloring composition is applied to a glass substrate or the like, and the waiting time from application of the coloring composition to exposure (PCD: Post Coating Delay) and exposure The stability and characteristic dependence of the pattern shape, etc., and the line width sensitivity stability with respect to the waiting time (PED: Post Exposure Delay) from the time to the heat treatment are improved. In addition, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked. Further, variation in development time and development residue are suppressed.

<Binder resin>
The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400-700 nm. In addition, the transmittance is preferably 95% or more. In terms of curing properties, binder resins include, for example, thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. In addition, the active energy ray-curable resin may have an active energy ray-reactive functional group in a thermoplastic resin or a thermosetting resin. In terms of physical properties, binder resins include alkali-soluble resins and the like. Alkali solubility is for imparting development solubility in an alkali development step during production of a color filter, which will be described later, and an acidic group is required.

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

Below, the binder resin that can be used in the coloring composition of the present invention will be described in detail.

[Thermoplastic resin]
Thermoplastic resins include, for example, acrylic resin, butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd Resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.
Alkali-soluble thermoplastic resins include, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Alkali-soluble thermoplastic resins include, for example, acrylic resins having acidic groups, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and the like. Among these, an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer are preferred from the standpoint of improving developability, heat resistance and transparency.

[Active energy ray-curable alkali-soluble resin]
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked by the effect of the active energy ray, thereby increasing the crosslink density and improving chemical resistance.

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

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acid.

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

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

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

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

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

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

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

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

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

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

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

[Alkali-soluble resin having no ethylenically unsaturated double bond]
The coloring composition herein can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of cure of the coating.

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 30,000 or less, and 4,000, in order to impart alkali developing solubility. 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 from 50 to 200 (KOHmg/g) in order to impart solubility in alkali development, preferably from 70 to 180, more preferably from 90 to 170. is. If the acid value is less than 50, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

Each raw material used for synthesizing the binder resin can be used alone or in combination of two or more.

[Thermosetting compound]
In the present invention, a thermosetting compound can be used in combination with the thermoplastic resin as the binder resin. When producing a color filter using the coloring composition 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. Pigment agglomeration during baking of the filter segment is suppressed, and the effect of improving the contrast ratio can be 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, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. Epoxy compounds and oxetane compounds are preferably used in the coloring composition of the present invention.

The content of the binder resin used in preparing the colored composition is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, with respect to 100 parts by mass of the coloring agent. When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

<Resin Dispersant>
The coloring composition of the present invention can contain a resin type dispersant. The dispersant has a colorant-affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and adsorbs to the added colorant to stabilize dispersion on the colorant carrier. It works to transform. Specific examples of resin-type dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof Oily dispersants such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more. It is not necessarily limited to these.

Among the above resin-type dispersants, the viscosity of the dispersion is lowered and high dispersion stability is exhibited by adding a small amount of the resin-type dispersant. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing nitrogen-containing heterocycles are well known.

When a resin-type dispersant is used in combination in the present invention, one having an acidic substituent is preferred, and among these, one having an aromatic carboxyl group is particularly preferred because it has a particularly large effect of preventing reaggregation of the colorant after dispersion. As a resin-type dispersant having an aromatic carboxy group, WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2009-155406, JP-A-2010-185934 , but not limited to those described in JP-A-2011-157416.

The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass, and more preferably in an amount of about 5 to 100 parts by mass based on the total amount of the coloring agent.

<Other coloring agents>
The colored composition of the present invention can contain other colorants as necessary within a range that does not impair the effects of the present invention. Other colorants may be pigments or dyes, and may be used alone or in combination of two or more. Specific examples of other colorants are shown below, but are not limited thereto.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP-A-2014-134712, pigments described in JP-A-6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 254, 269, 272, 291, 295, 296, the pigment described in JP-A-2014-134712, the pigment described in Japanese Patent No. 6368844 Yes, more preferably C.I. I. Pigment Red 177, 254, 269, 272, 291, 295, 296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844.

Examples of red dyes include xanthene-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, and anthraquinone-based dyes. Specifically, C.I. I. Salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338 are included.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP-A-2012-226110. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233, 234, pigments described in JP-A-2012-226110.

As an orange pigment, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and the like. Preferably C.I. I. Pigment Orange 71 and 73.

Orange dyes and/or yellow dyes include quinoline dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, and methine dyes.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

<Organic solvent>
The coloring composition of the present invention contains an organic solvent. This facilitates adjustment of the viscosity of the composition.

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

Among the above organic solvents, in the case of coating applications, it is preferable to include an organic solvent having a boiling point of 120° C. or higher and 180° C. or lower at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

(Photosensitive coloring composition)
The coloring composition of the present invention can further contain a polymerizable compound and/or a photopolymerization initiator. Thereby, it can be used as a photosensitive coloring composition.

<Polymerizable compound>
The polymerizable compound contained in the coloring composition of the present invention includes monomers or oligomers that are cured by ultraviolet light, heat, or the like to form a transparent resin.

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

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

Photopolymerizable monomers having an acid group include, for example, polyhydric alcohols and (meth)acrylic acid esters of free hydroxyl group-containing poly(meth)acrylates and dicarboxylic acids; Examples thereof include esterified products with hydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , malonic acid, succinic acid, glutaric acid, free carboxyl group-containing monoesters with dicarboxylic acids such as phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Monohydroxy monoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, and the like can be mentioned.

(Polymerizable compound having urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. and polyfunctional urethane acrylates obtained by

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

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

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

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

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

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

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

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

The content of the photopolymerization initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the colorant. When blended in an appropriate amount, the photocurability and developability are further improved.

<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.

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.

A sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol chain transfer agent>
The 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 photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen, so 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 thiol groups are preferred. More preferred are polyfunctional aliphatic thiols having 4 or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the substrate.

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

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the nonvolatile matter of the coloring composition. When contained in an appropriate amount, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

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

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

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

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

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1,1 ,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- 2H-benzotriazol-2-yl)phenyl]propionate. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate ester reaction product, 2,4-bis "2-hydroxy-4- butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

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

<Antioxidant>
The 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, so that the transmittance of the coating film can be improved. . 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 cause yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

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

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

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

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

<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. Various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants and anionic surfactants can be used as the leveling agent.

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 with respect to the total solid content of the coloring composition of the present invention, and more It is preferably 0.005 to 1.0% by mass. Within this range, the coating properties 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.

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

<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 with the adhesion improving agent, the reproducibility of fine lines is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy mercaptos such as silane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureides such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as , 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the 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.

<Method for producing colored composition>
The coloring composition of the present invention contains a coloring agent, a dispersing agent, a coloring agent carrier such as a binder resin, and/or a solvent, preferably together with a dispersing aid (pigment derivative or surfactant), kneader, two kneaders. It can be produced by finely dispersing using various dispersing means such as a 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 coloring agents and the like may be dispersed in the coloring agent carrier at the same time, or may be mixed separately dispersed in the coloring agent 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 photosensitive colored composition (resist material), it can be prepared as a solvent-developable or alkali-developable colored 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.

<Removal of coarse particles>
The coloring composition of the present invention is separated from coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.1 μm or more, by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, or the like. It is preferable to remove coarse particles of 5 μm or more 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.

<Water content in the coloring composition>
The coloring composition of the present invention preferably has a water content of 0.1 to 2.0% by mass or less relative to the total amount of the coloring composition. When the water content is within the above range, the coloring composition is excellent in dispersion stability and sensitivity even after being stored for a long time.
The water content is more preferably 0.1 to 1.8% by mass or less, more preferably 0.1 to 1.6% by mass or less, relative to the total amount of the coloring composition. If the content of water is sufficiently small within this range, problems with dispersion stability and sensitivity are less likely to occur even after long-term storage.

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

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

<Specific metal atom in the coloring composition>
The coloring composition of the present invention contains metal components containing a small amount of Li, Na, K, Cs, Mg, Ca, Fe, Cr, and Zr (hereinafter also referred to as specific metal atoms) in addition to the constituent components of the colorant. sometimes. If there are many metal components containing these specific metal atoms, storage stability may be inhibited, heat resistance may be lowered, and sensitivity may be lowered when prepared in the form of the above-mentioned photosensitive coloring composition. be.
In addition, a color filter prepared using a colored composition containing a large amount of metal components containing such specific metal atoms may generate foreign matter, and as a result, tends to cause a decrease in transmittance. The total content of specific metal atoms in the metal component contained in the coloring composition of the present invention is preferably 1 to 1000 mass ppm with respect to the entire coloring composition.

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

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

In addition, when metal atoms such as Ni, Zn, Cu, Al, Fe, Pt, and Co are included in part of the colorant structure, these metal atoms not forming part of the colorant structure are present. sometimes. The smaller the number of such metal atoms, the better, and they can be removed in the same manner as the specific metal atoms by the following method. Furthermore, it is preferable that the concentration of Mn, Cs, Ti, Si, Pd, and the like mixed in with materials (for example, catalysts) used in the manufacturing process of various raw materials of the coloring composition is low.

Various raw materials contained in the coloring composition or methods for removing metal atoms mixed from the apparatus during the manufacturing process include JP 2010-83997, JP 2018-36521, JP 7-198928, JP JP-A-8-333521, a method of washing with water according to JP-A-2009-7432, etc., a method of removing magnetic foreign matter by a magnet described in JP-A-2011-48736, etc., and a single or a plurality of methods are appropriately selected. use.

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

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

(color filter)
Next, the color filter of the present invention will be explained. The color filter of the present invention comprises a red filter segment, a green filter segment and a blue filter segment. Also, the color filter may further comprise a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

<Manufacturing method of color filter>
A color filter can be manufactured by a printing method or a photolithography method. Formation of filter segments by a printing method can be patterned simply by repeating printing and drying of a coloring composition prepared as a printing ink, and therefore, as a method for producing color filters, it is low cost and excellent in mass productivity. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to have a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and it is also possible to adjust the viscosity of the ink using a dispersant or an extender.

When the filter segment is formed by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern provided in contact or non-contact with the film. After that, the film is immersed in a solvent or alkaline developer or sprayed with a developer to remove the uncured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote polymerization of the colored resist material, heating may be applied as necessary. According to the photolithographic method, it is possible to manufacture a color filter with higher accuracy than the printing method.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method, etc. in addition to the above methods, and the colored composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which filter segments are formed in advance on the surface of a removable transfer base sheet, and the filter segments are transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed can be used, but is not limited to these. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment may be formed. An overcoat film, a transparent conductive film, and the like are formed on the color filter of the present invention, if necessary.

The color filter of the present invention can also be used for manufacturing color liquid crystal display devices, color solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and the like.

(sensor)
The sensor of the invention comprises the color filter segment of the invention. The configuration of the sensor of the present invention is a configuration provided with the color filter segment of the present invention, and is not particularly limited as long as it functions as a sensor. Examples of the configuration include the following.
A plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like are provided on a substrate, and on the photodiodes and the transfer electrodes, A light shielding film made of tungsten or the like with an opening only in the light receiving portion of the photodiode, and a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving portion of the photodiode, It is a configuration having the color filter of the present invention on the device protective film.
Furthermore, 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 inorganic materials play the role of extracting signals to the outside, and in principle, it is possible to achieve an aperture ratio of 100% for incident light. Since the organic photoelectric conversion film is a structure-free continuous film and can be laid on a CMOS signal readout substrate, it does not require an expensive microfabrication process and is suitable for miniaturization of filter segments.
Arrangement of the color filters 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 and comparative examples, "parts" means "mass parts".

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

(Compound identification method)
MALDI TOF-MS spectra were used to identify the compounds used in the present invention. The MALDI TOF-MS spectrum was obtained using a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics, and the compound obtained was identified by matching the molecular ion peak of the mass spectrum obtained in the negative mode with the mass number obtained by calculation. identified.

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

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

Next, the production of the binder resin solution, the resin-type dispersant solution, and the dye derivative used in Examples and Comparative Examples will be described.

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

<Production of resin type dispersant solution>
(Preparation of resin type dispersant solution 1)
10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, 40 parts of tert-butyl methacrylate, 20 parts of n-butyl acrylate, tert- 20 parts of butyl acrylate and 50 parts of propylene glycol monomethyl ether acetate were charged, and the atmosphere was purged with nitrogen gas.
The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 100 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst are added and reacted at 100° C. for 7 hours. rice field. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the reaction is terminated. A resin-type dispersant solution 1 having an acidic functional group with a molecular weight of 70 mgKOH/g and a weight average molecular weight of 8,600 was obtained.

<Production of dye derivative>
(Production of dye derivative A)
With reference to Synthesis Example 3 of Japanese Patent No. 5748665, a dye derivative A represented by the following structure was produced.

Dye derivative A

(Production of dye derivative B)
With reference to Production Example 6 of Japanese Patent No. 4983061, Dye Derivative B represented by the following structure was produced.

Dye derivative B

(Production of dye derivative C)
With reference to Production Example 3 of Japanese Patent No. 1863188, Dye Derivative C represented by the following structure was produced.

Dye derivative C

<Production of diketopyrrolopyrrole pigment>
[Example 1]
(Production of diketopyrrolopyrrole pigment (1-1))
200 parts of tert-amyl alcohol dehydrated with molecular sieves and 163 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere, and the mixture was heated to 100° C. with stirring to form an alcoholate solution. prepared. On the other hand, 100 parts of tert-amyl alcohol dehydrated with molecular sieves, 89.8 parts of diisopropyl succinate, and 100 parts of 2-fluoro-4-methylbenzonitrile were added to a glass flask and dissolved by heating to 90°C with stirring. and a solution of these mixtures was prepared. A heated solution of this mixture was uniformly added dropwise to the above alcoholate solution heated to 100° C. over 2 hours with vigorous stirring. 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, 300 parts of methanol, 1200 parts of water, and 304 parts of acetic acid were added to a glass-made jacketed reactor 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 filtered at 5° C. and washed with 500 parts of methanol and 2000 parts of water to obtain a red paste. This paste was redispersed in 1,600 parts of methanol cooled to 0° C. and 1,600 parts of water, and stirred at 5° C. for 3 hours. Subsequently, after filtering the suspension, it is washed with 500 parts of methanol and 2000 parts of water. A crude ketopyrrolopyrrole pigment (1-1) was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified by the agreement between the molecular ion peak of the mass spectrum obtained and the mass number obtained by calculation.
Furthermore, a mixture of 100 parts of crude diketopyrrolopyrrole pigment (1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol was kneaded at 60° C. for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). . Next, this kneaded product was put into 5 liters of hot water and stirred for 1 hour while being heated to 70° C. to form a slurry. After filtration, washing with 6 L of water was repeated three times to remove sodium chloride and diethylene glycol, followed by drying and pulverization to obtain 95 parts of diketopyrrolopyrrole pigment (1-1).

[Examples 2 to 25]
(Production of diketopyrrolopyrrole pigments (1-2 to 25))
2-fluoro-4-methylbenzonitrile was changed to a benzonitrile of the following general formula (6) in which Z ¹ to Z ⁵ are substituents listed in Table 2, and diisopropyl succinate and sodium -tert-amyl alkoxide were changed to the following Diketopyrrolopyrrole pigments (1-2 to 25) were obtained in the same manner as in Example 1, except that the amounts shown in Table 2 were changed.

general formula (6)

[Example 26]
(Production of diketopyrrolopyrrole pigment (1-26))
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, in reaction vessel 2, 100 parts of tert-amyl alcohol, 78.5 parts of the following intermediate 1 compound synthesized by the same method as in Tetrahedron, 58 (2002) 5547-5565, and 3-fluoro-4-methylbenzonitrile 45.9 parts were dissolved by heating and added dropwise to reaction vessel 1 over 2 hours. After reacting at 120° C. for 10 hours, the mixture was cooled to 60° C., 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol to obtain a diketopyrrolopyrrole pigment (1-26). .

Intermediate 1

[Example 27]
(Production of diketopyrrolopyrrole pigment (1-27))
Diketopyrrolopyrrole pigment (1-27) in the same manner as in Example 26 except that 45.9 parts of 3-fluoro-4-methylbenzonitrile was changed to 51.5 parts of 3-chloro-4-methylbenzonitrile got

<Adjustment of pigment composition (P)>
[Example 28]
(Preparation of pigment composition (P-1))
A mixture of 90 parts of diketopyrrolopyrrole pigment (1-4), 10 parts of dye derivative A, 1000 parts of sodium chloride, and 120 parts of diethylene glycol is kneaded at 60° C. for 6 hours using a stainless steel 1-gallon kneader (Inoue Seisakusho). bottom. Next, this kneaded product was put into 5 liters of hot water and stirred for 1 hour while being heated to 70° C. to form a slurry. After removing sodium chloride and diethylene glycol by repeating filtration and washing with water, the residue was dried and pulverized to obtain 95 parts of a pigment composition (P-1).

[Example 29]
(Preparation of pigment composition (P-2))
A pigment composition (P-2) was obtained in the same manner as in Example 28, except that the dye derivative A was changed to the dye derivative B.

[Example 30]
(Preparation of pigment composition (P-3))
A pigment composition (P-3) was obtained in the same manner as in Example 28, except that the dye derivative A was changed to the dye derivative C.

<Production of coloring composition>
[Example 101]
(Preparation of coloring composition (RP-1))
After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a coloring composition (RP-1).
Diketopyrrolopyrrole pigment (1-1) 12.6 parts Dye derivative A 0.7 parts Dye derivative B 0.7 parts Resin type dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether Acetate 68.0 parts The water content was 1.1% and the total amount of specific metal atoms was 190 ppm with respect to the entire coloring composition (RP-1).

[Examples 102 to 130]
(Preparation of colored composition (RP-2 to 30))
Coloring compositions (RP-2 to 30) was produced.

[Example 131]
(Preparation of coloring composition (RP-31))
After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a coloring composition (RP-1).
Diketopyrrolopyrrole pigment (1-1) 12.6 parts Dye derivative A 0.7 parts Dye derivative B 0.7 parts Resin type dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether Acetate 67.0 parts Ion-exchanged water 1.0 parts With respect to the entire coloring composition (RP-31), the water content was 2.3%, and the total amount of specific metal atoms was 185 ppm.

[Example 132]
(Preparation of coloring composition (RP-32))
A molecular sieve was added to the coloring composition (RP-1), and the mixture was allowed to stand for 24 hours and filtered to obtain a coloring composition (RP-32).
The water content was 0.2% and the total amount of specific metal atoms was 175 ppm with respect to the entire coloring composition (RP-32).

(Purification 1 of diketopyrrolopyrrole pigment (1-1))
In the production of diketopyrrolopyrrole pigment (1-1), the same operation as in Example 1 was performed except that washing with 6 L of water three times was changed to washing with 3 L of water once.

(Purification 2 of diketopyrrolopyrrole pigment (1-1))
In the production of diketopyrrolopyrrole pigment (1-1), the same operation as in Example 1 was performed except that washing with 6 L of water three times was changed to washing with 6 L of deionized water three times.

[Example 133]
(Preparation of coloring composition (RP-33))
Coloring composition in the same manner as the coloring composition (RP-1) except that the diketopyrrolopyrrole pigment (1-1) was changed to the compound obtained in Purification 1 of the diketopyrrolopyrrole pigment (1-1) product (RP-33) was obtained.
The water content was 1.2% and the total amount of specific metal atoms was 1070 ppm with respect to the entire coloring composition (RP-33).

[Example 134]
(Preparation of coloring composition (RP-34))
Coloring composition in the same manner as the coloring composition (RP-1) except that the diketopyrrolopyrrole pigment (1-1) was changed to the compound obtained in Purification 2 of the diketopyrrolopyrrole pigment (1-1) product (RP-34) was obtained.
The water content was 1.0% and the total amount of specific metal atoms was 50 ppm with respect to the entire coloring composition (RP-34).

[Comparative Example 101]
(Preparation of coloring composition (RP-35))
C.I. I. Pigment Red 254 (BASF "Irgazin RED L3630") was used to prepare a coloring composition (RP-35) in the same manner as in Example 101.

[Comparative Example 102]
(Preparation of coloring composition (RP-36))
Pigment (1-1) was mixed with C.I. I. A coloring composition (RP-36) was prepared in the same manner as in Example 101 except that Pigment Red 272 (BASF "Irgazin RED K3800") was used.

[Comparative Example 103]
(Preparation of coloring composition (RP-37))
A colored composition (RP-37) was prepared in the same manner as in Example 101, except that the pigment (1-1) was changed to a diketopyrrolopyrrole pigment represented by the following formula (2).

formula (2)

<Dispersion stability evaluation>
(Measurement of initial viscosity and rate of thickening over time)
For the viscosity of the coloring composition, the initial viscosity at 25° C. was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) on the day of preparation of the coloring composition. Then, for those left at 40 ° C. for 7 days counting from the day of coloring composition preparation, after returning the sample temperature to 25 ° C., the viscosity over time is measured according to the above viscosity measurement method, and the viscosity increase rate over time from the following formula asked for
Thickening rate over time = (viscosity over time) / (initial viscosity) x 100 (%)

(Evaluation of initial viscosity and rate of thickening over time)
Dispersion stability was evaluated based on the rate of increase in viscosity over time. Table 4 shows the results. If the viscosity increase rate over time is 80% or more and less than 120%, it can be practically endured. If the viscosity is reduced or increased beyond this range, the coloring composition cannot be applied under the same coating conditions when applied to the glass substrate, resulting in productivity problems. More preferably, it is in the range of 90% or more and less than 110%.
○: Time-dependent viscosity increase rate of 90% or more and less than 110%
△: 80% or more and less than 90% of viscosity increase over time, or 110% or more and less than 120%
×: Less than 80% thickening rate over time, or 120% or more

As shown in Table 4, the coloring composition using the diketopyrrolopyrrole pigment of the present invention exhibits excellent dispersion stability.

<Production of yellow colored composition>
(Preparation of colored composition (YP-1))
After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a coloring composition (YP-1).
C. I. Pigment Red Yellow 139 12.6 parts ("Cinilex (R) Yellow SY3C" manufactured by CINIC)
Pigment derivative C 1.4 parts Resin type dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether acetate 68.0 parts

<Production of photosensitive coloring composition>
[Example 201]
(Preparation of photosensitive coloring composition (RR-1))
The following mixture was uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (RR-1). The mixing ratio of the coloring composition (RP-1) and the coloring composition (YP-1) was adjusted so that the transmittance at 530 nm of the coating film was 5% when the transmittance at 400 nm was 5%.

Coloring composition (RP-1) and coloring composition (YP-1) total 72.86 parts binder resin solution 1 1.40 parts photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M-402") 1 .70 parts photopolymerization initiator (manufactured by BASF "IRGACURE OXE-02") 0.17 parts propylene glycol monomethyl ether acetate 23.87 parts

[Examples 202 to 230, Comparative Examples 201 to 203]
(Preparation of photosensitive coloring composition (RR-2 to 33))
The coloring composition (RP-1) was changed to the coloring composition shown in Table 5, and the coloring composition (YP- 1) to prepare a photosensitive coloring composition (RR-2 to 33) in the same manner as in Example 201, except that the mixing ratio was changed.

<Dispersion stability evaluation>
The dispersion stability of the resulting photosensitive coloring composition was measured in the same manner as for the dispersion stability of the coloring composition, and evaluated on a three-grade scale according to the following criteria.
○: Time-dependent viscosity increase rate of 95% or more and less than 105%
Δ: Time-dependent thickening rate of 90% or more and less than 95%, or 105% or more and less than 110%
×: Less than 90% thickening rate over time, or 110% or more

<Color strength evaluation>
The obtained photosensitive coloring composition was coated on a 6-inch glass wafer with a flattening film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) by spin coating, and pre-baked at 100 ° C. It was heat-treated on a hot plate for 6 minutes. Further, the coated film was cured in an oven at 230° C. for 1 hour to form a 1.0 μm flattening film to obtain a wafer with a flattening film. Next, the resulting resist material was applied onto a flattening film-attached glass wafer by a spin coater, and pre-baked by heat treatment on a hot plate at 100° C. for 1 minute. 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 through a photomask for forming 1.0 μm square pixels. gone. The exposed coating film was puddle-developed with an organic alkaline developer for 1 minute. After the puddle development, it was rinsed with pure water for 20 seconds using a spin shower, and then washed with pure water for 20 seconds. After that, water droplets remaining on the wafer were blown off with high-pressure air, and the substrate was naturally dried to form a square pixel pattern. After that, it was dried by heating at 230° C. for 20 minutes to prepare an evaluation substrate. At the time of preparation, adjustment was made by changing the rotation speed of spin coating so that the transmittance at 530 nm was 5%.
The coloring strength of this coating film was evaluated in three grades according to the following criteria.
○: film thickness is less than 0.55 μm
Δ: film thickness is 0.55 μm or more and less than 0.60 μm ×: film thickness is 0.60 μm or more

<Transmittance evaluation>
The transmittance of the previous coating film was evaluated in three grades according to the following criteria.
○: Transmittance at 600 nm is 90% or more △: Transmittance at 600 nm is 85% or more and less than 90% ×: Transmittance at 600 nm is less than 85%

Table 5 shows the evaluation results of the photosensitive coloring composition.

As described above, the diketopyrrolopyrrole pigment of the present invention can provide a photosensitive coloring composition exhibiting excellent coloring power, transmittance and dispersion stability.

Furthermore, by using these photosensitive coloring compositions, it is possible to provide a color filter for an image sensor with improved film thickness, improved color separation, and improved color reproducibility, and a sensor.

Claims (9)

A diketopyrrolopyrrole pigment characterized by being represented by the following general formula (1).

General formula (1)

[In the general formula (1), X ¹ and X ² each independently represent a fluorine, chlorine or bromine atom; R ¹ and R ² each independently represent a carbon atom optionally having a substituent represents an alkyl group of numbers 1 to 10; n ¹ and m ¹ each independently represent an integer of 1 to 4, n ² and m ² each independently represent an integer of 0 to 5, and n ¹ +m ¹ and n ² +m ² are integers of 5 or less . ]
A diketopyrrolopyrrole pigment characterized by being represented by the following general formula (2).
general formula (2)

[In general formula (2), Y ¹ to Y ³ each independently represent a hydrogen atom, X ¹ or R ¹ ; Y ⁴ to Y ⁶ each independently represent a hydrogen atom, X ² or R ² . X ¹ and X ² are each independently a fluorine, chlorine or bromine atom; R ¹ and R ² are each independently an optionally substituted alkyl group having 1 to 10 carbon atoms; be. However, at least one of Y ¹ to Y ³ is X ¹ and at least one is R ¹ . ] A pigment composition comprising the diketopyrrolopyrrole pigment according to claim 1 or 2 and a dye derivative. 4. A coloring composition comprising the diketopyrrolopyrrole pigment according to claim 1 or 2 or the pigment composition according to claim 3, and an organic solvent. 5. The colored composition according to claim 4, further comprising a photopolymerizable monomer and/or a photopolymerizable initiator. The coloring composition according to claim 4 or 5, wherein the water content in the coloring composition is 0.1 to 2.0% by mass with respect to the entire coloring composition. The coloring composition contains a metal component containing metal atoms selected from Li, Na, K, Cs, Mg, Ca, Fe, Cr, and Zr, and the metal in the metal component for the entire coloring composition The coloring composition according to any one of claims 4 to 6, wherein the total amount of atoms is 1 to 1000 mass ppm. A color filter having a coating formed from the colored composition according to any one of claims 4 to 7 on a substrate. A sensor comprising the color filter according to claim 8 .