TW202336165A - Diketopyrrolopyrrole pigment, pigment composition, colored composition, color filter, and sensor - Google Patents

Abstract

The purpose of the present invention is to provide a diketopyrrolopyrrole pigment that has both high coloring power and high transmittance as a red colorant, and further has excellent dispersion stability. Furthermore, the purpose of the present invention is to provide a pigment composition using said pigment, a colored composition, a color filter, and a sensor. The aforementioned problems are solved by a diketopyrrolopyrrole pigment characterized by being represented by general formula (1). [In general formula (1), A1 and A2 are each independent and represent a five-membered or six-membered ring that may have a substituted group, and the atoms forming the ring are each independent and may be carbon atoms, oxygen atoms, or sulfur atoms. R1 and R2 are each independent and represent hydrogen atoms, an alkyl group having 1-10 carbon atoms that may have a substituted group, or halogen atoms.].

Description

Diketopyrrolopyrrole pigment, pigment composition, coloring composition, color filter and sensor

The invention relates to a diketopyrrolopyrrole pigment, a pigment composition, a coloring composition, a color filter and a sensor.

In recent years, due to the popularity of digital cameras and camera-equipped mobile phones, there has been a demand for image sensors such as C-MOS (Complementary Metal Oxide Semiconductor) and CCD (Charge Coupled Device). substantial growth. These image sensors are generally equipped with color filters including additively mixed primary color filter segments (filter segments) of B (blue), G (green), and R (red) on their light receiving elements. slices for color decomposition.

Color filters for image sensors are required to be thinned or to have improved color resolution and color reproducibility, and the coloring composition used to form the filter segments of each color needs to have high tinting power and high transmittance. In particular, in order to increase the coloring power of the coloring composition, the concentration of the colorant is increased or a coloring agent with high coloring power is used.

Previously, C.I. Pigment Red 254 was used as a red colorant in the manufacture of red filter segments. However, the coloring power was not satisfactory in response to the strong thin film requirements in recent years. In addition, as a red colorant with high coloring power, the use of C.I. Pigment Red 272 or the diketopyrrolopyrrole pigment as described in Patent Document 3 has been studied. However, when the concentration is increased, the stability of the dispersion is poor and the transmission rate is 600 nm or more. Issues such as low rates. [Prior art documents] [Patent Document]

[Patent Document 1] International Publication No. 2021/166859 [Patent Document 2] International Publication No. 2020/040043 [Patent Document 3] International Publication No. 2019/059075

[Problem to be solved by the invention]

An object of the present invention is to provide a diketopyrrolopyrrole pigment that has both high coloring power and high transmittance as a red colorant and has excellent dispersion stability. In addition, the object is to provide a pigment composition, a colored composition, a color filter, and a sensor using the pigment. [Means to solve the problem]

As a result of repeated efforts in research, the inventors found that by using a specific diketopyrrolopyrrole pigment as a red colorant, high tinting power and high transmittance were achieved, and excellent dispersion stability was achieved, and the present invention was completed.

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

General formula (1) [Chemical formula 1] [In the general formula (1), A ¹ and A ² each independently represent a five-membered ring or a six-membered ring that may have a substituent, and the atoms forming the ring are each independently a carbon atom, an oxygen atom, or a sulfur atom; R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a halogen atom]

In addition, the present invention relates to a diketopyrrolopyrrole pigment characterized by being represented by the following general formula (2).

General formula (2) [Chemical formula 2] [In the general formula (2), X ¹ to X ⁶ are each independently -CR ⁵ R ⁶ -, -C(=O)-, -C(=S)-, an oxygen atom, or a sulfur atom; R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a halogen atom, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent. Alkyl group, or phenyl group which may have a substituent]

In addition, the present invention relates to a pigment composition characterized by containing the diketopyrrolopyrrole pigment and a pigment derivative.

In addition, the present invention relates to a colored composition characterized by containing the diketopyrrolopyrrole pigment or the pigment composition, and an organic solvent.

In addition, the present invention relates to a colored composition characterized by further containing a photopolymerizable monomer and/or a photopolymerizable initiator.

In addition, the present invention relates to a color filter having a film formed of the coloring composition on a base material.

In addition, the present invention relates to a sensor having the color filter. [Effects of the invention]

According to the present invention, it is possible to provide a diketopyrrolopyrrole pigment that has both high coloring power and high transmittance and has excellent dispersion stability. In addition, a pigment composition, a colored composition, a color filter, and a sensor using the pigment can be provided.

Each component of the present invention will be described below. Furthermore, in this application, when expressed as "(meth)acrylyl", "(meth)acrylic acid", "(meth)acrylic acid", "(meth)acrylate", or " In the case of "(meth)acrylamide", unless otherwise specified, it means "acrylyl and/or methacrylate", "acrylic and/or methacrylic", "acrylic and /or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide". Furthermore, "C.I." listed in this specification refers to Color Index (C.I.).

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

General formula (1) [Chemical formula 3] [In the general formula (1), A ¹ and A ² each independently represent a five-membered ring or a six-membered ring that may have a substituent, and the atoms forming the ring are each independently a carbon atom, an oxygen atom, or a sulfur atom; R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a halogen atom]

The five-membered ring or six-membered ring which may have a substituent is represented by a group selected from -CR ⁷ R ⁸ -, =CR ⁹ -, -C(=O)-, -C(=S)-, -O-, or - A five-membered ring or a six-membered ring formed by at least one of the groups formed by S-. R ⁷ to R ⁹ are substituents of a five-membered ring or a six-membered ring, and examples thereof include alkyl groups with 1 to 10 carbon atoms, trifluoromethyl, halogen atoms, nitro groups, cyano groups, carboxamide groups, and sulfamide groups. group or an alkoxy group having 1 to 4 carbon atoms, etc., but is not limited to these.

The "alkyl group" of the alkyl group having 1 to 10 carbon atoms which may have a substituent may be linear or branched. Examples thereof include: methyl, ethyl, propyl, isopropyl, and butyl. , isobutyl, second butyl, third butyl, pentyl, n-hexyl, heptyl, octyl, decyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2 -Ethylhexyl etc. In addition, from the viewpoint of coloring power or dispersion stability, the carbon number is preferably 1 to 5, and more preferably 1 to 3 carbon atoms. Examples of "substituted alkyl group" include: trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3- Tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methyl oxybenzyl, etc., but are not limited to these.

Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, an amide carboxyl group, an amide sulfonyl group, Phenyl group with substituents such as 1 to 4 alkoxy groups. More specifically, phenyl, p-methylphenyl, 4-tert-butylphenyl, p-nitrophenyl, p-methoxyphenyl, p-chlorophenyl, 2,4-dichloro Phenyl, 3-aminoformylphenyl, etc., but are not limited to these.

From the viewpoint of coloring power or dispersion stability, it is preferable that at least one of the atoms forming the five-membered ring or the six-membered ring is an oxygen atom or a sulfur atom, and more preferably it is a two-membered ring represented by the following general formula (1a). Ketopyrrolopyrrole pigments.

General formula (1a) [Chemical formula 4] [In the general formula (1a), a ¹ and a ² each independently represent a five-membered ring or a six-membered ring that may have a substituent, and the atoms forming the ring are each independently a carbon atom, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent an oxygen atom or a sulfur atom; R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms that may have a substituent, or a halogen atom]

In addition, from the viewpoint of coloring power or transmittance, the diketopyrrolopyrrole pigment in the present invention is preferably of general formula (2).

General formula (2) [Chemical formula 5] [In the general formula (2), X ¹ to X ⁶ are each independently -CR ⁵ R ⁶ -, -C(=O)-, -C(=S)-, an oxygen atom, or a sulfur atom; R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a halogen atom, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent. Alkyl group, or phenyl group which may have a substituent]

When X ¹ to X ⁶ are any one of -CR ⁵ R ⁶ -, -C(=O)-, -C(=S)-, oxygen atom, or sulfur atom, excellent coloring power is shown , transmittance, and dispersion stability. Among them, from the viewpoint of coloring power or dispersion stability, it is preferable that at least one of X ¹ to X ⁶ be an oxygen atom or a sulfur atom, and more preferably X ³ and X ⁶ are oxygen atom or sulfur atom.

Specific examples of the diketopyrrolopyrrole pigment of the present invention are listed below, but are not limited to these.

General formula (3) [Chemical formula 6]

[Table 1] Table 1 diketopyrrolopyrrole pigment Z ¹ Z ² diketopyrrolopyrrole pigment Z ¹ Z ² (1-1) (1-11) (1-2) (1-12) (1-3) (1-13) (1-4) (1-14) (1-5) (1-15) (1-6) (1-16) (1-7) (1-17) (1-8) (1-18) (1-9) (1-19) (1-10) (1-20) Table 1 (continued) diketopyrrolopyrrole pigment Z ¹ Z ² diketopyrrolopyrrole pigment Z ¹ Z ² (1-21) (1-31) (1-22) (1-32) (1-23) (1-33) (1-24) (1-34) (1-25) (1-35) (1-26) (1-36) (1-27) (1-37) (1-28) (1-38) (1-29) (1-39) (1-30) (1-40)

From the viewpoint of coloring power, transmittance and dispersion stability, among the above-mentioned structures, diketopyrrolopyrrole pigments (1-1 to 1-21) and the like are preferred, and (1-6 to 1 -21), etc., particularly preferably (1-6, 1-9~1-16, 1-19~1-21), etc.

<Production method of diketopyrrolopyrrole pigment> The method for producing the diketopyrrolopyrrole pigment of the present invention is not particularly limited, and it can be produced most simply by using a succinic acid diester synthesis method. That is, 1 mole of the succinic acid diester and 2 moles of the benzonitrile compound represented by the following general formula (4) are mixed in an inert organic solvent such as tertiary pentanol, an alkali metal or an alkali metal alkoxide. The condensation reaction is carried out at a high temperature of 80°C to 110°C to generate an alkali metal salt of the diketopyrrolopyrrole compound, and then, for the alkali metal salt of the diketopyrrolopyrrole compound, water, alcohol , acid, etc. are protonated, thereby obtaining various diketopyrrolopyrrole pigments. At this time, the size of the primary particle diameter obtained can be controlled by the temperature during protonation, the type, ratio or amount of water, alcohol or acid.

General formula (4) [Chemical formula 7] [In the general formula (4), A ³ represents a five-membered ring or a six-membered ring which may have a substituent, and the atoms forming the ring are independently carbon atoms, oxygen atoms or sulfur atoms; R ¹⁰ represents a hydrogen atom, which may have a substitution Alkyl group or halogen atom with 1 to 10 carbon atoms]

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

＜Pigment Derivatives＞ The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of dye derivatives include compounds having an acidic substituent such as a sulfo group, a carboxyl group, or a phosphate group, and amine salts thereof, and compounds having a basic substituent such as a sulfonamide group or a tertiary amine group at the terminal, Compounds with neutral substituents such as phenyl or phthalimide alkyl groups. Examples of organic pigments include: diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, ionone pigments, perylene pigments, thiazide-indigo pigments, and trioxazine pigments. Azine pigments, benzimidazolone pigments, indole pigments such as benzisoindole, isoindoline pigments, isoindolinone pigments, quinphthalone pigments, naphthol pigments, reducing pigments Pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, etc.

Specific examples of diketopyrrolopyrrole dye derivatives include Japanese Patent Application Laid-Open No. 2001-220520, Manual No. WO2009/081930, Manual No. WO2011/052617, Manual No. WO2012/102399, and Japanese Patent Application Laid-Open No. 2017- Pigment derivatives described in Publication No. 156397; examples of phthalocyanine-based dye derivatives include Japanese Patent Laid-Open No. 2007-226161, Manual WO2016/163351, Japanese Patent Laid-Open No. 2017-165820, and Japanese Patent No. 5753266 The pigment derivatives described in; the anthraquinone-based pigment derivatives include Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, and Japanese Patent Application Laid-Open No. 1000-245501. Pigment derivatives described in Publication No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, and Manual No. WO2009/025325; examples of quinacridone-based pigment derivatives include Japanese Patent Application Laid-Open No. Sho 48-54128, Japan Pigment derivatives described in Japanese Patent Application Laid-Open No. 03-9961 and Japanese Patent Application Publication No. 2000-273383; examples of the dioxazine-based pigment derivatives include those described in Japanese Patent Application Laid-Open No. 2011-162662; Examples of thiazine-indigo dye derivatives include those described in Japanese Patent Application Laid-Open No. 2007-314785; examples of triazine-based dye derivatives include Japanese Patent Application Publication No. 61-246261 and Japanese Patent Application Publication No. 11-11 Pigment derivatives described in Japanese Patent Application Publication No. 199796, Japanese Patent Application Publication No. 2003-165922, Japanese Patent Application Publication No. 2003-168208, Japanese Patent Application Publication No. 2004-217842, and Japanese Patent Application Publication No. 2007-314681; Examples of benzoisoindole-based dye derivatives include those described in Japanese Patent Application Laid-Open No. 2009-57478; examples of quinophthalone-based dye derivatives include Japanese Patent Application Publication No. 2003-167112 and Japanese Patent Application Laid-Open No. 2003-167112. Pigment derivatives described in Japanese Patent Application Publication No. 2006-291194, Japanese Patent Application Publication No. 2008-31281, and Japanese Patent Application Publication No. 2012-226110; examples of naphthol-based pigment derivatives include Japanese Patent Application Publication No. 2012-208329, Pigment derivatives described in Japanese Patent Laid-Open No. 2014-5439; azo dye derivatives include those described in Japanese Patent Laid-Open No. 2001-172520 and Japanese Patent Laid-Open No. 2012-172092; Examples of acidic substituents include dye derivatives described in Japanese Patent Application Laid-Open No. 2004-307854; examples of basic substituents include Japanese Patent Application Publication No. 2002-201377, Japanese Patent Application Publication No. 2003-171594, and Japanese Patent Application Publication No. 2003-171594. Pigment derivatives described in Japanese Patent Application Publication No. 2005-181383 and Japanese Patent Application Publication No. 2005-213404. Furthermore, in these documents, pigment derivatives having an acidic group or a base in the organic pigment residue may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, etc. Compounds with substituents such as sexual groups and neutral groups have the same meaning as pigment derivatives.

The pigment derivative contained in the pigment composition of the present invention is preferably a diketopyrrolopyrrole pigment derived from an organic pigment residue from the viewpoint of coloring power, miniaturization efficiency, and dispersion stability. , anthraquinone pigments, quinophthalone pigments or pigment derivatives of azo pigments.

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

These pigment derivatives can be used individually or in mixture of 2 or more types.

The pigment composition of the present invention can be prepared by simply mixing diketopyrrolopyrrole pigment powder and pigment derivative powder. The pigment composition can be obtained by the following methods: using a dissolver, a high-speed mixer, a homogeneous mixer, Methods for mechanically mixing pigment powder and pigment derivative powder using kneaders, roller mills, attritors, sand mills, various pulverizers, etc.; added to the suspension system of the pigment using water or organic solvents A method of depositing the pigment derivative on the surface of the pigment using a solution containing a pigment derivative; a method of co-dissolving organic pigments and pigment derivatives in a solvent with strong solubility such as sulfuric acid and co-deposition using a poor solvent such as water, etc.

＜Miniaturization of pigments＞ The diketopyrrolopyrrole pigment used in the pigment composition of the present invention is preferably used for miniaturization. The method of miniaturization is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution and precipitation methods can be used. As exemplified in the present invention, salt grinding can be performed using a kneader method, which is a type of wet grinding. (salt milling) processing, etc. to refine it.

The so-called salt mill treatment is as follows: using a kneader, a two-rod roll mill, a three-rod roll mill, a ball mill, a grinder, a sand mill, and a planetary mixer. A batch or continuous kneading machine such as a machine is used to mechanically knead the mixture of pigments, water-soluble inorganic salts and water-soluble organic solvents while heating, and then remove the water-soluble inorganic salts and water-soluble organic solvents by washing with water. 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 grinding. By optimizing the conditions for the salt grinding treatment of pigments, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate, etc. can be used. In terms of price, sodium chloride (table salt) is preferably used. In terms of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and most preferably in an amount of 300 to 1,000 parts by mass based on 100 parts by mass of the pigment.

The water-soluble organic solvent functions to moisten the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is an organic solvent that is dissolved (mixed) in water and does not substantially dissolve the inorganic salt used. Among them, since the temperature rises during salt grinding and the solvent is easily evaporated, a high boiling point solvent with a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isoamyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol Ethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass relative to 100 parts by mass of the pigment, and most preferably in an amount of 50 to 500 parts by mass.

During salt milling treatment, in order to improve the kneading efficiency, pigment derivatives can also be added, which is very effective in miniaturizing and granulating the pigment. The usage amount of the pigment derivative is preferably in a range that does not affect the color tone, that is, in a range of 0.5% by mass to 40% by mass relative to 100% by mass of the pigment.

In addition, when carrying out salt grinding treatment, resin can also be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified by natural resin, etc. can be used. The resin used is preferably solid and water-insoluble at room temperature, and is further preferably partially soluble in the organic solvent. The usage amount of the resin is preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

By subjecting the diketopyrrolopyrrole pigment to salt milling treatment, it can be more uniformly refined and improve the coloring power, transmittance, and dispersion stability in a well-balanced manner.

The average primary particle diameter of the diketopyrrolopyrrole pigment of the present invention is preferably in the range of 30 nm to 200 nm. If the average primary particle diameter is 200 nm or more, the coloring power will be high, but the transmittance will be low. If the average primary particle diameter is less than 30 nm, the transmittance will increase, but the resistance will decrease. In addition, as the specific surface area of the colorant increases, the cohesive force increases and the dispersibility or storage stability of the coloring composition deteriorates.

The average primary particle diameter is measured using the following method: using a Transmission Electron Microscope (TEM) H-7650 manufactured by Hitachi High-Technologies Co., Ltd. and directly measuring it based on electron micrographs The size of the primary particle. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is used as the particle diameter of the pigment primary particles. Next, for 100 or more pigment particles, the volume (weight) of each particle is determined by approximating a cube of the determined particle diameter, and the volume average particle diameter is regarded as the average primary particle diameter.

(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. Binder resin, resin dispersant, and other colorants may also be included as needed.

By subjecting the raw materials to dispersion treatments such as wet dispersion using two-rollers, three-rollers, and beads, for example, pigment derivatives are adsorbed on the surface of the pigment. The surface of the pigment is polar, which promotes the adsorption of the resin-type dispersant and improves the interaction with the pigment, The compatibility of pigment derivatives, resin-type dispersants, organic solvents, and other additives improves the dispersion stability or time-dependent viscosity stability when making colored compositions. In addition, due to improved compatibility, the coating film when the colored composition is applied to a glass substrate or the like has excellent stability over time, compared with the waiting time from application of the colored composition to exposure (post-coating delay). (PCD: Post Coating Delay)) or the waiting time from exposure to heat treatment (Post Exposure Delay (PED: Post Exposure Delay)), the stability of the pattern shape, characteristic dependence, or line width sensitivity stability become better . In addition, since the pigment surface is adsorbed and covered with the pigment derivative and the resin-type dispersant, crystallization caused by the aggregation or sublimation of the pigment during heating and baking of the coating film can be suppressed. Furthermore, deviations in development time and development residue are also suppressed.

＜Binder resin＞ The binder resin is a resin with a transmittance of 80% or more in all wavelength regions from 400 nm to 700 nm. Furthermore, the transmittance is preferably 95% or more. In terms of curability, examples of the binder resin include thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. Furthermore, the active energy ray-curable resin may have an active energy ray-reactive functional group in the thermoplastic resin or thermosetting resin. In terms of physical properties, examples of the binder resin include alkali-soluble resins and the like. Alkali solubility is used to provide development solubility in an alkali development step when producing a color filter described later, and an acidic group is required.

The binder resin can be used alone or in combination of two or more kinds.

Hereinafter, the binder resin usable in the colored composition of the present invention will be described in detail.

[Thermoplastic resin] Examples of thermoplastic resins include acrylic resin, butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (High Density Polyethylene, HDPE ), low density polyethylene (LDPE), polybutadiene, and polyimide resin, etc. Examples of the thermoplastic resin having alkali solubility include resins having acidic groups such as carboxyl groups and styrene groups. Examples of the alkali-soluble thermoplastic resin include acrylic resin having an acidic group, styrene/styrenesulfonic acid copolymer, ethylene/(meth)acrylic acid copolymer, and the like. Among these, an acrylic resin and a styrene/styrenesulfonic acid copolymer having an acidic group are preferred in terms 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. The ethylenically unsaturated double bond can be introduced, for example, by the method (i) (ii) shown below. Utilizing the effect brought by active energy rays, the resin is three-dimensionally cross-linked, thereby increasing the cross-link density and improving chemical resistance.

[Method (i)] Method (i) is, for example, a method of adding an ethylenically unsaturated side chain epoxy group to a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. The carboxyl group of the double-bonded unsaturated monobasic acid; then, the polybasic acid anhydride is reacted with the generated hydroxyl group, thereby introducing the ethylenically unsaturated double bond and the carboxyl group.

Examples of the ethylenically unsaturated monomer having an epoxy group include: (glycidylmeth)acrylate, methylglycidyl(meth)acrylate, 2-glycidoxyethyl(meth)acrylate, 3,4-epoxybutyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate. Among these, from the viewpoint of reactivity with unsaturated monobasic acid, glycidyl (meth)acrylate is preferred.

Examples of unsaturated monobasic acids include: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, (meth)acrylic acid's α-position haloalkyl group, alkoxy group, Halogen, nitro, cyano substituents and other monocarboxylic acids, etc.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Furthermore, the number of carboxyl groups may be increased, and if necessary, tricarboxylic anhydrides such as trimellitic anhydride may be used, or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

Examples of other monomers include the following. Examples include: (methyl)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate )Isobutyl acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate )Lauryl acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Phenoxyethyl ester, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate (meth)acrylate, etc. )Acrylate, Or (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide Amine, diacetone (meth)acrylamide, or acrylamide and other (meth)acrylamides, Styrenes such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, etc. Vinyl ethers, fatty acid vinyl esters such as vinyl acetate or vinyl propionate, etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1 ,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4 ,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylene N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6- Trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide Imine, N-bromomethyl-2,3-dichloromaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-3 -Maleimide propionate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimidecaproate, N- [4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and other N-substituted maleimines, ethylene oxide (EO) Modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) modification of phenol (methane acrylate, EO or propylene oxide (PO)-modified (meth)acrylate of p-cumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified nonylphenol Quality (meth)acrylate, etc.

A method similar to the method (i) is, for example, a method in which a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer is added to a cyclic structure. The ethylenically unsaturated monomer of oxygen group introduces ethylenically unsaturated double bonds and carboxyl groups.

[Method (ii)] Method (ii) is a method of copolymerizing an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group and a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group and another monomer. side chain hydroxyl groups react.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate or 3-hydroxypropyl(meth)acrylate, (meth)acrylate 2-hydroxybutyl methacrylate or 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono (Meth)acrylate and other hydroxyalkyl methacrylates. In addition, polyether mono(meth)acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, or Polyester mono(meth)acrylate obtained by adding polyγ-valerolactone, polyε-caprolactone, and/or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred. In addition, from the perspective of sensitivity, it is preferred to use two Those with more than 6 hydroxyl groups and less than 6 are more preferably glycerol mono(meth)acrylate.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloxyethyl isocyanate, 2-(meth)acryloxyethyl isocyanate, or 1,1- Bis[methacryloxy]ethyl isocyanate, etc.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimines and alkyleneoxy group-containing monomers. , ethylenically unsaturated monomers containing phosphate groups, ethylenically unsaturated monomers containing carboxyl groups, etc. Examples of N-substituted maleimines include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bis Maleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Leimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N, N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl) maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide Amine, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimide-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide Imide caproate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine, etc. Examples of monomers containing an alkyleneoxy group include EO modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, and ethoxylated phenyl acrylate. Ester, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of p-cumylphenol, EO-modified nonylphenol ( Meth)acrylate, PO-modified (meth)acrylate of nonylphenol, etc.

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

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

[Alkali-soluble resin without ethylenically unsaturated double bonds] The colored composition of this specification may contain an alkali-soluble resin which does not have an ethylenically unsaturated double bond in order to adjust the hardening degree of a film.

In order to impart alkali development solubility, 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, more preferably 4,000 or more and 20,000 or less. In addition, the value of Mw/Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, making it difficult for the exposure pattern to remain. If it exceeds 40,000, the solubility for alkali development decreases, residues are generated, and the linearity of the pattern deteriorates. In order to provide alkali development solubility, the acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g), preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. . If the acid value is less than 50, the solubility for alkali development decreases, residues are generated, and the linearity of the pattern deteriorates. If it exceeds 200, the adhesion to the substrate decreases and the exposure pattern becomes difficult to remain.

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

[Thermosetting compound] In the present invention, the binder resin can be used in combination with a thermoplastic resin, and further includes a thermosetting compound. When the colored composition of the present invention is used to produce a color filter, by including a thermosetting compound, the following effect can be obtained: a reaction occurs during calcination of the filter segment to increase the cross-linking density of the coating film, thereby increasing the cross-linking density of the coating film. The heat resistance of the filter section is improved, pigment aggregation when the filter section is fired is suppressed, and the contrast ratio is improved.

The thermosetting compound may be a low molecular compound or a resin-like high molecular weight compound. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the colored composition of the present invention, it is preferred to use an epoxy compound and an oxetane compound.

The content of the binder resin used in producing the coloring composition is preferably 20 to 400 parts by mass relative to 100 parts by mass of the colorant, more preferably 50 to 250 parts by mass. If it is contained in an appropriate amount, not only can a film be easily formed, but also good color characteristics can be easily obtained.

＜Resin type dispersant＞ The colored composition of the present invention may contain a resin dispersant. The dispersant includes a colorant-affinity moiety that has the property of adsorbing the added colorant and a moiety that is compatible with the colorant carrier, and functions to adsorb the added colorant and stabilize the dispersion in the colorant carrier. role. As the resin-type dispersant, specifically, polycarboxylic acid esters such as polyurethane and polyacrylate can be used; unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid Ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters or modified products of these; by poly(lower alkylene imine) ) and oily dispersants such as amide or its salt formed by reaction with polyester having free carboxyl groups; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, Styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins or water-soluble polymer compounds; polyester series, modified polyacrylate series, ethylene oxide/propylene oxide addition Compounds, phosphate esters, etc., these may be used alone or in mixture of two or more types, but are not necessarily limited to these.

Among the resin-type dispersants, in order to lower the viscosity of the dispersion and exhibit dispersion stability with a small amount of addition, it is well known that there are graft copolymers containing nitrogen atoms; or graft copolymers containing three atoms in the side chain. Grade amine groups, quaternary ammonium bases, nitrogen atom-containing acrylic block copolymers containing functional groups such as nitrogen-containing heterocycles, and urethane polymer dispersants, etc.

When a resin-type dispersant is used together in the present invention, a resin-type dispersant having an acidic substituent is preferred. Among them, a resin-type dispersant having an aromatic carboxyl group has the effect of preventing the re-aggregation of the dispersed colorant. Extra large, therefore extra good. Examples of the resin-type dispersant having an aromatic carboxyl group include WO2008/007776, Japanese Patent Laid-Open No. 2008-029901, Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2009-155406, and Japan Patent Laid-Open No. 2009-155406. The resin-type dispersants described in Japanese Patent Application Laid-Open No. 2010-185934 and Japanese Patent Application Publication No. 2011-157416 are not limited to these.

The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass relative to the total amount of the colorant, and from the viewpoint of film-forming properties, it is more preferably used in an amount of about 5 to 100 parts by mass.

＜Other colorants＞ The colored composition of the present invention may contain other colorants as necessary within the 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. As other colorants, specific examples are shown below, but they are not limited to these.

Examples of red pigments include: C.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 Japanese Patent Laid-Open No. 2014-134712, Japanese Patent No. 6368844 Pigments, etc. described in . Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Red 48: 1, 122, 177, 224, 242, 254, 269, 272, 291 is preferred , 295, 296, the pigment described in Japanese Patent Publication No. 2014-134712, the pigment described in Japanese Patent Publication No. 6368844, and more preferably C.I. Pigment Red 177, 254, 269, 272, 291, 295, 296. The pigments described in Japanese Patent Application Laid-Open No. 2014-134712 and the pigments described in Japanese Patent Application No. 6368844.

Examples of red dyes include xanthene-based dyes, azo-based dyes (pyridone-based dyes, barbituric acid-based dyes, metal complex dyes, etc.), disazo-based dyes, anthraquinone-based dyes, and the like. Specific examples include salt-forming compounds of xanthene-based acid dyes such as C.I. acid red 52, 87, 92, 289, and 338.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34 , 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93 ,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,138 ,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, 234, pigments described in Japanese Patent Application Laid-Open No. 2012-226110, etc. Preferable are pigments described in C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, 234 and Japanese Patent Application Laid-Open No. 2012-226110.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and the like. C.I. Pigment Orange 71 and 73 are preferred.

Examples of orange dyes and/or yellow dyes include quinoline dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, methine dyes, and the like.

Examples of purple pigments include: C.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, etc. Among these, from the viewpoint of the heat resistance, light resistance, and transmittance of the filter segment, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

＜Organic solvent＞ The colored composition of the present invention contains an organic solvent. This makes it easy to adjust the viscosity of the composition.

Examples of organic solvents include: ethyl lactate, butyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol (1,3-butanediol), 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-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate , 4-Heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butanol, n-butyl Benzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, 2nd butylbenzene, 3rd butylbenzene, γ- Butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethyl glycol 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 mono Methyl 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, cyclopentanone, 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, glyceryl triacetate, 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, methyl isobutyl ketone, methylcyclohexanol, n-pentyl acetate, n-butyl acetate, acetic acid Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

Among the organic solvents, when used for coating, it is preferable to include an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less in terms 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, and diethylene glycol monomethyl ether are preferred. , diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., preferably propylene glycol monomethyl ether ethyl acid ester, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc.

(Photosensitive coloring composition) The colored composition of the present invention may further contain a photopolymerizable monomer and/or a photopolymerizable initiator. Thereby, it can be used as a photosensitive coloring composition.

＜Photopolymerizable monomer＞ The photopolymerizable monomer contained in the colored composition of the present invention includes a monomer or oligomer that is cured by ultraviolet rays to form a transparent resin.

Examples of photopolymerizable monomers include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 2-hydroxypropyl Cyclohexyl acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol diacrylate (Meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol Alcohol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate acrylate, isocyanuric acid EO modified tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecyl (meth)acrylate, (meth)acrylate of methylolated melamine, epoxy Various acrylates and methacrylates such as (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Pentaerythritol triethylene ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

(Photopolymerizable monomer with acid group) The photopolymerizable monomer may contain a photopolymerizable monomer having an acid group. Examples of acidic groups include: sulfonic acid group, carboxyl group, phosphate group, etc.

Examples of the photopolymerizable monomer having an acid group include: esterified products of poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; polycarboxylic acids, and ( Esterified products of monohydroxyalkyl methacrylate, etc. Specific examples include: trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. Mono-hydroxyl oligoacrylates or monohydroxyl oligomethacrylates, and monoesters containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; Propane-1 ,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3, 4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid and other tricarboxylic acids, and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacrylic acid 2 - Monohydroxymonoacrylates such as hydroxypropyl ester or oligomeric esters of monohydroxymonomethacrylates containing free carboxyl groups, etc.

(Photopolymerizable monomer with urethane bond) The photopolymerizable monomer may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the monomer include polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with (meth)acrylate having a hydroxyl group, or polyfunctional isocyanate reacting with an alcohol and then reacting with an alcohol having a hydroxyl group. Polyfunctional urethane acrylate obtained by reacting (meth)acrylate, etc.

Examples of (meth)acrylates having a hydroxyl group include: (2-hydroxyethylmeth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tris(meth)acrylate. Meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol ring Oxypropane modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerin acrylate methacrylate, glycerol dimethacrylate, methacrylic acid 2 -Hydroxy-3-acrylylpropyl ester, reaction product of epoxy group-containing compound and carboxyl (meth)acrylate, hydroxyl-containing polyol polyacrylate, etc.

Examples of polyfunctional isocyanates include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The photopolymerizable monomer can be used alone or in combination of two or more types.

The blending amount of the photopolymerizable monomer is preferably 1% to 50% by mass, more preferably 2% to 40% by mass based on 100% by mass of non-volatile components of the coloring composition. If blended in an appropriate amount, the hardening and developability will be further improved.

＜Photopolymerizable initiator＞ Examples of photopolymerizable initiators include 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, and 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine propan-1-one, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-1-butanone, or 2- (Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other acetophenone compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ester, 4-benzene benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide or 3,3',4,4'-tetrakis Tributyl peroxycarbonyl) benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 , 4-diisopropyl thioxanthone or 2,4-diethyl thioxanthone and other thioxanthone compounds; 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-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1- base)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine or 2,4-trichloromethyl-(4' -Methoxystyryl)-6-triazine and other triazine compounds; 1,2-octanedione, 1-[4-(phenylsulfanyl)phenyl-,2-(O-benzoyl) oxime)] or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), etc. Oxime ester compounds; phosphine systems such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide Compounds; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate ester compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc. Among these, oxime ester compounds are preferred.

The photopolymerizable initiator can be used alone or in combination of two or more types.

(oxime ester compound) Oxime ester compounds absorb ultraviolet rays and cause the cleavage of the N-O bond of the oxime to generate imine radicals and alkoxy radicals. These free radicals are further decomposed to generate highly active free radicals, so patterns 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 become low and the hardening degree of the coating film may become low. However, the oxime ester compound has high quantum efficiency and can be suitably used.

Examples of oxime ester compounds include Japanese Patent Application Laid-Open No. 2007-210991, Japanese Patent Application Laid-Open No. 2009-179619, Japanese Patent Application Laid-Open No. 2010-037223, Japanese Patent Application Laid-Open No. 2010-215575, and Japanese Patent Application Laid-Open No. 2010-215575. The oxime ester-based photopolymerizable initiator described in Publication No. 2011-020998, etc.

The content of the photopolymerizable initiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass relative to 100 parts by mass of the colorant. If blended in an appropriate amount, the photohardenability and developability will be further improved.

＜Sensitizer＞ Furthermore, the colored composition of the present invention may contain a sensitizer. Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, and 1,2-diketones such as benzoyl and camphorquinone. Derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin Derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxocyanine derivatives and other polymethine pigments, acridine derivatives, azine derivatives, thiazine derivatives, oxanine derivatives Azine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetraphenyl Porphyrazine derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalinoporphyrazine derivatives, naphthalocyanine derivatives, Phthalocyanine derivatives, pyranium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, sulfur Spiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes or Michler's ketone derivatives, α-carboxylate, acylphosphine oxide, methyl phenyl glyoxylate), 9,10-phenanthrenequinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3'-tetrakis(tert-butylbutyl) Oxycarbonyl) benzophenone or 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone, 4,4'-bis(diethylamino) benzophenone, etc.

Among the sensitizers, sensitizers that can be particularly suitably sensitized include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. Furthermore, specifically, 2,4-diethylthiaxantrone, 2-chlorothiaxantrone, 2,4-dichlorothiaxantrone, 2-isopropylthiaxantrone, 4 -Isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethyl methylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3 , 6-dibenzoyl-N-ethylcarbazole, etc.

Furthermore, specifically, "Handbook of Pigments" compiled by Nobu Okawara et al. (1986, Kodan Co., Ltd.), "Chemistry of Functional Pigments" compiled by Nobu Okawara et al. (1981, CMC), Chusanro Ikemori et al. The sensitizers are described in "Special Functional Materials" edited by 1986, CMC, but are not limited to these. In addition, a sensitizer that exhibits absorption of light in the ultraviolet to near-infrared range may be included.

The sensitizer can be used individually or in combination of 2 or more types.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass relative to 100 parts by mass of the photopolymerizable initiator. If contained in an appropriate amount, curability and developability will be further improved.

＜Thercaptan chain transfer agent＞ The colored composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerizable initiator, it functions as a chain transfer agent during the radical polymerization process after light irradiation, generating thiyl radicals that are less susceptible to polymerization inhibition by oxygen. Therefore, the obtained colored composition becomes highly sensitive.

In addition, a polyfunctional aliphatic thiol having two or more thiol groups bonded to an aliphatic group such as a methylene group or an ethylidene group is preferred. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved and can be hardened from the surface of the pattern to the vicinity of the substrate.

Examples of polyfunctional thiols include: hexanedithiol, decanedithiol, 1,4-butanediol disulfiopropionate, 1,4-butanediol disulfioglycolate, Ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane trithiopropionate (3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, 1,4-dimethyl Mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferred examples include: ethylene glycol Alcohol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol chain transfer agent is preferably 0.1% by mass to 10% by mass, and more preferably 0.1% by mass to 3% by mass in 100% by mass of non-volatile components of the coloring composition. If contained in an appropriate amount, the light sensitivity and tapered shape will be improved, and wrinkles will be less likely to occur on the surface of the film.

＜Polymerization inhibitor＞ The colored composition of the present invention may contain a polymerization inhibitor. Thereby, photosensitivity due to diffracted light from the mask can be suppressed during exposure by photolithography, so that a pattern of a desired shape can be easily obtained.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, and 4-methylcatechol. , 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2 -n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol Alkyl catechol compounds such as butylcatechol, 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethyl Resorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol Phenol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkyl resorcinol compounds; methylhydroquinone, ethylhydroquinone, propylhydroquinone Alkyl hydroquinone compounds such as hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone; tributylphosphine, trioctylphosphine, tricyclohexyl Phosphine compounds such as phosphine, triphenylphosphine and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphites such as triphenylphosphite and trinonylphenylphosphite Compounds; pyrogallol, phloroglucin, etc.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 mass% based on 100% by mass of non-volatile components of the coloring composition. Within this range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

＜UV absorber＞ The colored composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, and salicylic acid ester compounds. compounds, cyanoacrylate compounds, salicylate compounds, etc.

The content of the ultraviolet absorber is preferably 5 to 70 mass% based on 100% by mass of the total of the photopolymerizable initiator and the ultraviolet absorber. If contained in an appropriate amount, the resolution after development will be further improved.

In addition, the total content of the photopolymerizable initiator and the ultraviolet absorber is preferably 1 to 20 mass% in 100 mass% of the nonvolatile components of the coloring composition. If contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzene Triazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 5% of 2-methoxy- 1-Methylethyl acetate with 95% phenylpropionic acid and 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy and C7- Mixture of 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- The reaction product of 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 2-(2H- Benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole-2 -yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro- 2H-benzotriazole-2-yl)-6-tert-butyl-4-methylphenol, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-[2-Hydroxy-5-[2-(methacryloxy)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. Other oligomer-type and polymer-type compounds having a benzotriazole structure may also be used.

Examples of triazine-based 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 ( The reaction product of 2-ethylhexyl)-glycidyl ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)- 1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6- Diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol, 2,4,6-tris(2- Hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. Other oligomer-type and polymer-type compounds having a triazine structure may also be used.

Examples of benzophenone compounds include: 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone. Ketone, 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, etc. Other oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the salicylate-based compound include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Other oligomer-type and polymer-type compounds having a salicylate structure may also be used.

＜Antioxidants＞ The colored composition of the present invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiator or thermosetting compound contained in the coloring composition from being oxidized and yellowed due to thermal hardening or the thermal step during annealing of indium tin oxide (ITO), thereby improving the The transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of cross-linked components in the coating film decreases. Therefore, if countermeasures such as the use of highly sensitive cross-linked components or the increase of the photopolymerizable initiator are taken, it is found that The phenomenon of enhanced yellowing during thermal steps. Therefore, by including an antioxidant to prevent yellowing caused by oxidation during the heating step, a high transmittance of the coating film can be obtained.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Furthermore, in this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

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

Antioxidants can be used alone or in combination of two or more types.

In addition, when the content of the antioxidant is 0.5% by mass to 5.0% by mass in 100% by mass of the solid content of the coloring composition, it is more preferable because the transmittance, spectral characteristics, and sensitivity are good.

＜Leveling agent＞ In order to improve the coating properties of the composition on the transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

When the colored composition of the present invention contains a surfactant, the added amount of the surfactant is preferably 0.001 mass % to 2.0 mass % based on the total solid content of the colored composition of the present invention, and more preferably 0.005% by mass to 1.0% by mass. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the coloring composition becomes good. The colored composition of the present invention may contain only one kind of surfactant, or may contain two or more kinds. When two or more types are included, it is preferable that the total amount falls within the above range.

＜Storage Stabilizer＞ In order to stabilize the viscosity of the composition over time, the colored composition of the present invention may contain a storage stabilizer. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid, and their methyl ethers, tert-butylcatechol, Tetraethylphosphine, tetraphenylphosphine and other organic phosphines, phosphites, etc. Based on the total amount of colorants (100% by mass), the storage stabilizer can be used in an amount of 0.1% to 10% by mass.

＜Adhesion improving agent＞ In order to improve the adhesiveness with the base material, the colored composition of the present invention may contain an adhesive improving agent such as a silane coupling agent. By improving the adhesion using an adhesion improving agent, the reproducibility of fine lines becomes better and the resolution is improved.

Examples of adhesion improving agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methyl Acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxysilane (meth)acrylic silanes such as methylpropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Epoxysilanes such as silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-amine Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-benzene Aminosilanes such as 3-aminopropyltrimethoxysilane and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; 3 -Mercapto groups such as mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl groups such as p-styryltrimethoxysilane; 3-ureidopropyltriethoxysilane Silane coupling agents such as urea-based ones; thioethers such as bis(triethoxysilylpropyl)tetrasulfide; isocyanates such as 3-isocyanatepropyltriethoxysilane and other silane coupling agents. The adhesion improving agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the colorant in the coloring composition. Within this range, the effect becomes larger, and the balance between adhesion, resolution, and sensitivity is good, so it is better.

＜Manufacturing method of coloring composition＞ The colored composition of the present invention can be preferably dispersed using various methods such as a kneader, a two-roller mill, a three-roller mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or a grinder. Means: The colorant is finely dispersed together with a dispersion aid (pigment derivative or surfactant) in a colorant carrier and/or solvent such as a dispersant and a binder resin (colorant dispersion). At this time, two or more colorants may be dispersed simultaneously in the colorant carrier, or those dispersed separately in the colorant carrier may be mixed. When the solubility of a coloring agent such as a dye is high, specifically, if the solubility in the solvent used is high, the colorant is dissolved by stirring, and no foreign matter is recognized, there is no need to carry out microfining as described above. Dispersed to make.

In addition, when used as a photosensitive coloring composition (resist material), it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the colorant dispersion, the photopolymerizable monomer and/or the photopolymerizable initiator, optional solvents, other dispersion aids, additives, etc. . The photopolymerizable initiator can be added at the stage of preparing the colored composition, or can be added to the prepared colored composition later.

＜Removal of coarse particles＞ The colored composition of the present invention is preferably centrifugal separation with a gravity acceleration of 3000 G to 25000 G, filtration using a sintered filter or a membrane filter, etc. to remove coarse particles of 5 μm or more, preferably 1 μm or more. Removal of coarse particles, preferably 0.5 μm or more, and mixed dust. As mentioned above, it is preferable that the colored composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Moisture content in coloring composition> The colored composition of the present invention preferably has a water content of 0.1 mass % to 2.0 mass % or less based on the total amount of the colored composition. When the content of water is within the above range, the dispersion stability and sensitivity will be excellent even after the coloring composition is stored over time. The water content is more preferably 0.1 mass% to 1.8 mass% or less, and further preferably 0.1 mass% to 1.6 mass% or less relative to the total amount of the coloring composition. If the content of water is sufficiently small within this range, problems in dispersion stability and sensitivity are less likely to occur even after storage over time.

The method of controlling the water content is not particularly limited, and known methods can be used. Examples include a method of producing a coloring composition while blowing dry inert gas, a method of adding molecular sieves to dehydrate the composition after production, and the like. Among them, a method of manufacturing while blowing dry inert gas is preferred.

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

＜Specific metal atoms in coloring compositions＞ In addition to the constituent components of the colorant, the colored composition of the present invention may also contain small amounts of Li, Na, K, Cs, Mg, Ca, Fe, Cr and Zr (hereinafter also referred to as specific metal atoms). metal composition. If a metal component containing these specific metal atoms is present in a large amount, the storage stability may be inhibited, the heat resistance may be reduced, or the sensitivity may be reduced when prepared in the form of the photosensitive coloring composition. In addition, a color filter produced using a colored composition in which a metal component containing a specific metal atom is present in a large amount may generate foreign matter, and as a result, the transmittance may be easily reduced. The total content of the specific metal atoms in the metal component contained in the colored composition of the present invention is preferably 1 mass ppm to 1000 mass ppm relative to the entire colored composition.

The total amount of specific metal atoms contained in the colored composition of the present invention is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less relative to the total coloring composition. In addition, the lower limit of the total amount of specific metal atoms is not particularly limited, but it is preferably 1 mass ppm or more, and more preferably 5 mass ppm or more based on the entire coloring composition. If it is within the above range, it is possible to obtain a colored composition that can suppress costs, is excellent in storage stability, and can form a color filter with little generation of foreign matter and less decrease 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 that do not form part of the colorant structure may be present. The number of such metal atoms is preferably small, and they can be removed by the following method in the same manner as the specific metal atoms. Furthermore, the concentration of substances such as Mn, Cs, Ti, Si, and Pd that may be mixed by materials (such as catalysts) used in the production steps of various raw materials of the coloring composition is also preferably low.

Examples of methods for removing various raw materials contained in the self-coloring composition or metal atoms mixed from equipment during the manufacturing process include Japanese Patent Application Laid-Open No. 2010-83997, Japanese Patent Application Laid-Open No. 2018-36521, and Japanese Patent Application Laid-Open No. 2018-36521. Methods using water washing described in Japanese Patent Application Laid-Open No. 7-198928, Japanese Patent Application Publication No. 8-333521, Japanese Patent Application Publication No. 2009-7432, etc., and methods using magnets described in Japanese Patent Application Publication No. 2011-48736 Methods such as the removal of magnetic foreign matter can be used alone or multiple methods can be used appropriately.

The content of specific metal atoms can be determined by inductively coupled plasma luminescence spectrometry (Inductively Coupled Plasma (ICP)).

<Amount of toluene in coloring composition> The coloring composition of the present invention may also contain toluene. When it is contained, the content of toluene is preferably 0.1 mass ppm 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, further preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and still more preferably 0.4 mass ppm or more.

(color filter) Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter section, a green filter section and a blue filter section. In addition, the color filter may further include a magenta filter section, a cyan filter section and a yellow filter section.

＜How to manufacture color filters＞ Color filters can be produced by printing or photolithography. Regarding the formation of filter segments by the printing method, patterning can be achieved by simply repeating printing and drying of a colored composition prepared as printing ink, so it is a low-cost and high-volume manufacturing method for color filters. Excellent 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 prevents the ink from drying or solidifying on the printing plate or blanket. In addition, it is also important to control the fluidity of the ink on the printing press. Dispersants or extender pigments can also be used to adjust the viscosity of the ink.

When the filter segment is formed by photolithography, a coating method such as spray coating, spin coating, slit coating, roll coating, etc. will be used as the solvent development type or alkali development type. The colored composition prepared by coloring the resist material is applied on the transparent substrate so that the dry film thickness becomes 0.2 μm to 5 μm. The film that has been dried as necessary is exposed (irradiated with radiation) through a mask having a predetermined pattern that is provided in a state of being in contact with or not in contact with the film. Then, the color filter can be manufactured by immersing it in a solvent or alkaline developer, or spraying the developer with spray, etc., to remove the unhardened portion to form the desired pattern. The same operation can then be repeated for other colors. . Furthermore, in order to promote the polymerization of the colored resist material, heating may be performed if necessary. According to the photolithography method, color filters with higher precision than the above-mentioned printing method can be produced.

During development, as an alkaline developer, aqueous solutions such as sodium carbonate and sodium hydroxide can be used, and organic bases such as dimethylbenzylamine and triethanolamine can also be used. In addition, defoaming agents or surfactants can also be added to the developer. Furthermore, in order to improve the exposure sensitivity, after the colored resist is coated and dried, a water-soluble or alkali-water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be coated and dried to form a protective layer that prevents the formation of oxygen. The film causes polymerization to retard and is then exposed to light.

In addition to the above-mentioned methods, the color filter of the present invention can also be produced by electrodeposition method, transfer method, inkjet method, etc., and the colored composition of the present invention can also be used in any method. Furthermore, the electrodeposition method is a method in which a transparent conductive film formed on a substrate is used to electrodeposit color filter segments on the transparent conductive film through electrophoresis of colloidal particles, thereby manufacturing a color filter. In addition, the transfer method is a method of forming a filter segment in advance on the surface of a releasable transfer base sheet and transferring the filter segment to a desired substrate.

The black matrix can be formed in advance before forming the filter segments of each color 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 it is not limited to these. In addition, a thin film transistor (TFT) may also be preformed on the transparent substrate or reflective substrate, and then filter segments of various colors may be formed. In addition, an overcoat film, a transparent conductive film, etc. may be formed on the color filter of the present invention if necessary.

The color filter of the present invention can also be used in the manufacture of 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 present invention includes the color filter segment of the present invention. The structure of the sensor of the present invention is not particularly limited as long as it includes the color filter segment of the present invention and functions as a sensor. Examples thereof include the following structures. The structure is as follows: on a substrate, there are a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and a transmission electrode including polycrystalline silicon, etc. The photodiode and the transmission electrode are provided with a light-shielding film containing tungsten or the like that is open only to the light receiving portion of the photodiode, and the light-shielding film is provided with a light-shielding film to cover the entire surface of the light-shielding film and the photodiode. A device protective film composed of silicon nitride or the like formed in the form of a light receiving portion, and the color filter of the present invention is provided on the device protective film. Furthermore, it may be a structure in which a light condensing unit (such as a microlens, etc.; the same applies below) is provided on the device protective film and below the color filter (side close to the substrate), or a light condensing unit is provided on the color filter. The structure of the unit, etc. Furthermore, the organic CMOS sensor is composed of a full-color photosensitive organic photoelectric conversion film as a thin film of the photoelectric conversion layer and a CMOS signal readout substrate, and carries an organic material that captures light and converts it into an electrical signal. It is a two-layer hybrid structure in which an inorganic material carries the function of exporting electrical signals to the outside. In principle, it can achieve an aperture ratio of 100% with respect to incident light. The organic photoelectric conversion film is a continuous film with a free structure and can be laid on a CMOS signal readout substrate. Therefore, it does not require expensive microfabrication processes and is suitable for miniaturization of filter segments. The arrangement of the color filters is not particularly limited, and known methods can be used. [Example]

Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto. In the examples and comparative examples, "part" means "part by mass".

(Acid value of resin dispersant and binder resin) The acid value of the resin-type dispersant and the binder resin was determined by potentiometric titration using a 0.1 N potassium hydroxide-ethanol solution. The acid value of the resin-type dispersant and binder resin represents the acid value of the non-volatile component. (Weight average molecular weight (Mw) of binder resin and resin dispersant) The weight average molecular weight (Mw) of the resin was measured using a TSKgel column (manufactured by Tosoh Corporation) and a gel permeation chromatograph (GPC) equipped with an RI detector (Tosoh Corporation). Manufactured by HLC-8120GPC) and measured using tetrahydrofuran (THF) as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene was measured.

(Method for identification of compounds) Matrix Assisted Laser Desorption Ionization-Time of Flight-Mass Spectrometry (MALDI TOF-MS) spectroscopy is used to identify the compounds used in the present invention. The MALDI TOF-MS spectrum uses the MALDI mass analysis device Autoflex III manufactured by Bruker-Daltonics, and is based on the obtained molecular ion peak of the mass spectrum in negative mode and calculation. The obtained mass numbers were consistent to identify the obtained compound.

(Measurement method of moisture content of coloring compositions) The moisture content (mg) was measured using a Karl Fischer titration device (volumetric titration moisture measuring device KF-06 manufactured by Mitsubishi Chemical Corporation), and the moisture content (%) was calculated by the following formula. Moisture content (%) = [moisture content (mg) / measured sample amount (mg)] × 100

(Method for measuring specific metal atoms in coloring compositions) The amount of specific metal atoms in the coloring composition was determined by decomposing the powder obtained by drying the coloring composition at 180°C using microwaves, and then using an ICP luminescence analysis device Varian 720- manufactured by Agilent Technologies. ES was measured.

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

＜Manufacture of adhesive resin solution＞ (Preparation of binder resin solution 1) Put 370 parts of cyclohexanone into a detachable four-necked flask including a thermometer, cooling tube, nitrogen gas introduction tube, dropping tube and stirring device, raise the temperature to 80°C, replace the nitrogen in the flask, and add it dropwise 18 parts of dicyclopentyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'- were added dropwise over 2 hours. A mixture of 2.0 parts of azobisisobutyronitrile. After the dropwise addition, the reaction was continued at 100° C. for 3 hours, and then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100° C. for 1 hour. Next, the container was replaced with air, and 0.5 part of tri-dimethylaminophenol and 0.1 part of hydroquinone were put into the container into 9.3 parts of acrylic acid (100% of the glycidyl group), and continued at 120°C. The reaction was carried out for 6 hours, and the reaction was terminated when the acid value of the solid content reached 0.5, and an acrylic resin solution was obtained. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled, dried by heating at 180°C for 20 minutes, and the nonvolatile content was measured. Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass. acetate to prepare adhesive resin solution 1. The weight average molecular weight (Mw) is 19,000.

＜Manufacture of resin-type dispersant solution＞ <Preparation of resin-type dispersant solution 1> Put 10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, and a third part of methacrylic acid into a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer. 40 parts of butyl ester, 20 parts of n-butyl acrylate, 20 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were replaced with nitrogen. Heat and stir the reaction vessel to 50°C, and add 12 parts of 3-mercapto-1,2-propanediol. The temperature was raised to 90° C., and a solution obtained by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added and reacted for 7 hours. By measuring the solid content, it was confirmed that 95% of the solution was reacted. Add 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, and heat at 100°C The reaction was carried out for 7 hours. By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified, the reaction was completed, and propylene glycol monomethyl ether acetate was added and diluted so that the solid content became 40% according to the solid content measurement, and the acid value was obtained. It is a resin-type dispersant solution 1 with an acidic functional group of 70 mgKOH/g and a weight average molecular weight of 8600.

＜Manufacture of Pigment Derivatives＞ (Manufacture of Pigment Derivative A) The dye derivative A represented by the following structure was produced with reference to Synthesis Example 3 of Japanese Patent No. 5748665.

Pigment Derivative A [Chemical 8]

(Manufacture of Pigment Derivative B) The dye derivative B represented by the following structure was produced with reference to Production Example 6 of Japanese Patent No. 4983061.

Pigment Derivative B [Chemical 9]

(Manufacturing of Pigment Derivative C) The dye derivative C represented by the following structure was produced with reference to Production Example 3 of Japanese Patent No. 1863188.

Pigment derivative C [Chemical 10]

<Manufacture of diketopyrrolopyrrole pigment> [Example 1] (Production of diketopyrrolopyrrole pigment (1-1)) In a nitrogen atmosphere, 200 parts of tertiary amyl alcohol dehydrated by molecular sieve and 153.8 parts of tertiary sodium amyl alkoxide were added to a stainless steel reaction vessel with a reflux tube, and heated to 100°C while stirring to prepare an alkoxide solution. On the other hand, 100 parts of tertiary pentanol dehydrated through molecular sieves, 84.7 parts of diisopropyl succinate, and 100 parts of benzonitrile compound (1) were added to a glass flask and heated to 90°C while stirring to dissolve them. , prepare solutions of these mixtures. The heated solution of this mixture was evenly added dropwise to the alkoxide solution heated to 100° C. over 2 hours while vigorously stirring. After the dropwise addition, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of the diketopyrrolopyrrole compound. Furthermore, 300 parts of methanol, 1200 parts of water, and 304 parts of acetic acid were added to the reaction vessel with a glass jacket, and the mixture was cooled to -10°C. To this cooled mixture, a small amount of the previously obtained diketopyrrolopyrrole compound cooled to 75° C. was added thereto gradually while using a high-speed stirrer and disperser to rotate a shear disk with a diameter of 8 cm at 4000 rpm. Alkali metal salt solution. At this time, the mixture containing methanol, acetic acid, and water was cooled so that the temperature of the mixture containing methanol, acetic acid, and water was always kept below -5° C., and the addition rate of the alkali metal salt of the diketopyrrolopyrrole compound at 75° C. was adjusted. Add in small amounts gradually over about 120 minutes. After the alkali metal salt is added, red crystals precipitate and a red suspension is generated. Then, the obtained red suspension was filtered at 5° C., and then 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 and 1,600 parts of water cooled to 0°C, and stirred at 5°C for 3 hours. Next, the suspension was filtered, washed with 500 parts of methanol and 2000 parts of water, and the obtained water paste of the diketopyrrolopyrrole compound was dried at 80° C. for 24 hours and pulverized. The diketopyrrolopyrrole pigment (1-1) was obtained. The result of mass analysis based on TOF-MS is to identify the obtained compound based on the consistency between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Benzonitrile compound (1) [Chemical 11]

[Example 2 to Example 40] (Production of diketopyrrolopyrrole pigments (1-2 to 1-40)) The benzonitrile compound (1) was changed to the following formula in which Z ¹ is the substituent listed in Table 2 The benzonitrile compound of the general formula (5) was prepared by the same method as in Example 1, except that diisopropyl succinate and sodium tert amyl alcoholate were changed to the amounts described in Table 2 below. Diketopyrrolopyrrole pigments (1-2 to 1-40) were obtained.

General formula (5) [Chemical formula 12]

[Table 2] Table 2 diketopyrrolopyrrole pigment Benzonitrile compound Diisopropyl succinate (part) Sodium tertiary amyl alcoholate (part) Z ¹ Example 1 (1-1) 84.7 153.8 Example 2 (1-2) 77.2 140.1 Example 3 (1-3) 70.1 127.2 Example 4 (1-4) 77.2 140.1 Example 5 (1-5) 57.5 104.3 Example 6 (1-6) 83.6 151.7 Example 7 (1-7) 83.6 151.7 Example 8 (1-8) 83.6 151.7 Example 9 (1-9) 82.5 149.7 Example 10 (1-10) 75.3 136.7 Table 2 diketopyrrolopyrrole pigment Benzonitrile compound Diisopropyl succinate (part) Sodium tertiary amyl alcoholate (part) Z ¹ Example 11 (1-11) 68.5 124.3 Example 12 (1-12) 84.8 153.9 Example 13 (1-13) 75.3 136.7 Example 14 (1-14) 54.8 99.5 Example 15 (1-15) 73.5 133.4 Example 16 (1-16) 75.3 136.6 Example 17 (1-17) 75.3 136.6 Example 18 (1-18) 75.3 136.6 Example 19 (1-19) 67.7 122.9 Example 20 (1-20) 56.8 103.1 Table 2 diketopyrrolopyrrole pigment Benzonitrile compound Diisopropyl succinate (part) Sodium tertiary amyl alcoholate (part) Z ¹ Example 21 (1-21) 76.2 138.4 Example 22 (1-22) 77.2 140.1 Example 23 (1-23) 70.9 128.6 Example 24 (1-24) 65.5 118.9 Example 25 (1-25) 76.2 138.4 Example 26 (1-26) 76.2 138.4 Example 27 (1-27) 76.2 138.4 Example 28 (1-28) 75.3 136.7 Example 29 (1-29) 50.6 91.8 Example 30 (1-30) 75.3 136.7 Table 2 diketopyrrolopyrrole pigment Benzonitrile compound Diisopropyl succinate (part) Sodium tertiary amyl alcoholate (part) Z ¹ Example 31 (1-31) 69.3 125.7 Example 32 (1-32) 69.2 125.7 Example 33 (1-33) 62.8 114.0 Example 34 (1-34) 62.8 114.0 Example 35 (1-35) 70.1 127.2 Example 36 (1-36) 78.2 141.9 Example 37 (1-37) 78.2 141.9 Example 38 (1-38) 77.2 140.1 Example 39 (1-39) 70.1 127.1 Example 40 (1-40) 79.2 143.8

[Example 41] (Production of finely divided diketopyrrolopyrrole pigment (2-1)) A mixture of 100 parts of 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, the kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating 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, and then dried and pulverized to obtain 95 parts of finely divided diketopyrrolopyrrole pigment (2-1).

[Example 42 to Example 80] (Production of finely divided diketopyrrolopyrrole pigments (2-2 to 2-40)) Except having changed the diketopyrrolopyrrole pigment (1-1) into (1-2 to 1-40), in the same manner as in Example 41, a finely divided diketopyrrolopyrrole pigment ( 2-2～2-40).

<Preparation of pigment composition (P)> [Example 81] (Preparation of finely divided pigment composition (P-1)) A mixture of 90 parts of diketopyrrolopyrrole pigment (1-9), 10 parts of pigment derivative A, 1,000 parts of sodium chloride, and 120 parts of diethylene glycol was mixed using a stainless steel 1-gallon kneader (Inoue Seisakusho). Knead at 60°C for 6 hours. Next, the kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. Filtration and water washing were repeated to remove sodium chloride and diethylene glycol, and then dried and pulverized to obtain 95 parts of a finely divided pigment composition (P-1).

[Example 82] (Preparation of finely divided pigment composition (P-2)) A refined pigment composition (P-2) was obtained in the same manner as in Example 81, except that the dye derivative A was changed to the dye derivative B.

[Example 83] (Preparation of finely divided pigment composition (P-3)) A refined pigment composition (P-3) was obtained in the same manner as in Example 81, except that the dye derivative A was changed to the dye derivative C.

＜Manufacture of coloring composition＞ [Example 101] (Preparation of coloring composition (RP-1)) The following mixture was stirred and mixed until it became uniform, and then an Eiger-mill (mini model M manufactured by Eiger Japan) was used using zirconia beads with a diameter of 0.5 mm. -250 MKII") was dispersed for 5 hours, and then filtered with a 5.0 μm filter to prepare a coloring composition (RP-1). Micronized diketopyrrolopyrrole pigment (2-1) 12.6 parts Pigment Derivative A 0.7 parts Pigment derivative B 0.7 parts Resin dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether acetate 68.0 parts The water content of the coloring composition (RP-1) as a whole is 1.1%, and the total amount of specific metal atoms is 190 ppm.

[Example 102 to Example 144] (Preparation of coloring compositions (RP-2 to RP-44)) In addition to changing the micronized diketopyrrolopyrrole pigment (2-1) to the micronized diketopyrrolopyrrole pigment, the micronized pigment composition, or the diketopyrrolopyrrole pigment described in Table 3, it is the same as Colored compositions (RP-1) were produced in the same manner as colored compositions (RP-2 to RP-44).

[table 3] table 3 coloring composition Pigments or pigment compositions Example 101 RP-1 Micronized diketopyrrolopyrrole pigment (2-1) Example 102 RP-2 Micronized diketopyrrolopyrrole pigment (2-2) Example 103 RP-3 Micronized diketopyrrolopyrrole pigment (2-3) Example 104 RP-4 Micronized diketopyrrolopyrrole pigment (2-4) Example 105 RP-5 Micronized diketopyrrolopyrrole pigments (2-5) Example 106 RP-6 Micronized diketopyrrolopyrrole pigments (2-6) Example 107 RP-7 Micronized diketopyrrolopyrrole pigments (2-7) Example 108 RP-8 Micronized diketopyrrolopyrrole pigments (2-8) Example 109 RP-9 Micronized diketopyrrolopyrrole pigments (2-9) Example 110 RP-10 Micronized diketopyrrolopyrrole pigment (2-10) Example 111 RP-11 Micronized diketopyrrolopyrrole pigment (2-11) Example 112 RP-12 Micronized diketopyrrolopyrrole pigment (2-12) Example 113 RP-13 Micronized diketopyrrolopyrrole pigment (2-13) Example 114 RP-14 Micronized diketopyrrolopyrrole pigment (2-14) Example 115 RP-15 Micronized diketopyrrolopyrrole pigment (2-15) Example 116 RP-16 Micronized diketopyrrolopyrrole pigment (2-16) Example 117 RP-17 Micronized diketopyrrolopyrrole pigment (2-17) Example 118 RP-18 Micronized diketopyrrolopyrrole pigment (2-18) Example 119 RP-19 Micronized diketopyrrolopyrrole pigment (2-19) Example 120 RP-20 Micronized diketopyrrolopyrrole pigment (2-20) Example 121 RP-21 Micronized diketopyrrolopyrrole pigment (2-21) Example 122 RP-22 Micronized diketopyrrolopyrrole pigment (2-22) Example 123 RP-23 Micronized diketopyrrolopyrrole pigment (2-23) Example 124 RP-24 Micronized diketopyrrolopyrrole pigment (2-24) Example 125 RP-25 Micronized diketopyrrolopyrrole pigment (2-25) Example 126 RP-26 Micronized diketopyrrolopyrrole pigment (2-26) Example 127 RP-27 Micronized diketopyrrolopyrrole pigment (2-27) Example 128 RP-28 Micronized diketopyrrolopyrrole pigment (2-28) Example 129 RP-29 Micronized diketopyrrolopyrrole pigment (2-29) Example 130 RP-30 Micronized diketopyrrolopyrrole pigment (2-30) Example 131 RP-31 Micronized diketopyrrolopyrrole pigment (2-31) Example 132 RP-32 Micronized diketopyrrolopyrrole pigment (2-32) Example 133 RP-33 Micronized diketopyrrolopyrrole pigment (2-33) Example 134 RP-34 Micronized diketopyrrolopyrrole pigment (2-34) Example 135 RP-35 Micronized diketopyrrolopyrrole pigment (2-35) Example 136 RP-36 Micronized diketopyrrolopyrrole pigment (2-36) Example 137 RP-37 Micronized diketopyrrolopyrrole pigment (2-37) Example 138 RP-38 Micronized diketopyrrolopyrrole pigment (2-38) Example 139 RP-39 Micronized diketopyrrolopyrrole pigment (2-39) Example 140 RP-40 Micronized diketopyrrolopyrrole pigment (2-40) Example 141 RP-41 Micronized pigment composition (P-1) Example 142 RP-42 Micronized pigment composition (P-2) Example 143 RP-43 Micronized pigment composition (P-3) Example 144 RP-44 Diketopyrrolopyrrole pigment (1-1)

[Example 145] (Preparation of coloring composition (RP-45)) The following mixture was stirred and mixed until it became uniform, and then an Eiger-mill (mini model M manufactured by Eiger Japan) was used using zirconia beads with a diameter of 0.5 mm. -250 MKII") was dispersed for 5 hours, and then filtered with a 5.0 μm filter to prepare a coloring composition (RP-45). Micronized diketopyrrolopyrrole pigment (2-9) 12.6 parts Pigment Derivative A 0.7 parts Pigment derivative B 0.7 parts Resin dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether acetate 67.0 parts Ion exchange water 1.0 parts The water content of the coloring composition (RP-45) as a whole is 2.4%, and the total amount of specific metal atoms is 190 ppm.

[Example 146] (Preparation of coloring composition (RP-46)) Molecular sieves were put into the colored composition (RP-9) and left for 24 hours. The resulting substance was filtered to prepare a colored composition (RP-46). The water content of the entire coloring composition (RP-46) is 0.4%, and the total amount of specific metal atoms is 170 ppm.

(Purification of finely divided diketopyrrolopyrrole pigment (2-9) 1) In the production of the finely divided diketopyrrolopyrrole pigment (2-9), the same procedure 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. operate.

(Purification of finely divided diketopyrrolopyrrole pigment (2-9) 2) In the production of the finely divided diketopyrrolopyrrole pigment (2-9), the same procedure as in Example 1 was carried out except that the washing with 6 L of water three times was changed to the washing with 6 L of ion-exchange water three times. Same operation.

[Example 147] (Preparation of coloring composition (RP-47)) In addition to the compound obtained in the purification 1 of changing the fine diketopyrrolopyrrole pigment (2-9) into the fine diketopyrrolopyrrole pigment (2-9), the coloring composition (RP-9) A colored composition (RP-47) was obtained in the same manner. The water content of the coloring composition (RP-47) as a whole is 1.5%, and the total amount of specific metal atoms is 1030 ppm.

[Example 148] (Preparation of coloring composition (RP-48)) In addition to the compound obtained in Purification 2 of changing the fine diketopyrrolopyrrole pigment (2-9) into the fine diketopyrrolopyrrole pigment (2-9), the same as the colored composition (RP-9) A colored composition (RP-48) was obtained in the same manner. The water content of the entire coloring composition (RP-48) is 1.0%, and the total amount of specific metal atoms is 60 ppm.

[Comparative Example 101] (Preparation of coloring composition (RP-49)) The diketopyrrolopyrrole pigment (1-1) was changed to C.I. Pigment Red 254 (BASF's "Irgazin RED L3630") and the same method as in Example 41 was used. A colored composition (RP-49) was produced in the same manner as in Example 101, except that a finely divided pigment was used instead of the finely divided diketopyrrolopyrrole pigment (2-1).

[Comparative Example 102] (Preparation of coloring composition (RP-50)) The diketopyrrolopyrrole pigment (1-1) was changed to C.I. Pigment Red 272 (BASF's "Irgazin RED K3800") and the same method as in Example 41 was used. A colored composition (RP-50) was produced in the same manner as in Example 101, except that a finely divided pigment was used instead of the finely divided diketopyrrolopyrrole pigment (2-1).

[Comparative Example 103] (Preparation of coloring composition (RP-51)) A pigment obtained by changing the diketopyrrolopyrrole pigment (1-1) to a diketopyrrolopyrrole pigment represented by the following formula (2) and pulverizing it in the same manner as in Example 41 was used. A colored composition (RP-51) was produced in the same manner as in Example 101, except that the finely divided diketopyrrolopyrrole pigment (2-1) was used.

Formula (2) [Chemistry 13]

＜Evaluation of dispersion stability＞ (Measurement of initial viscosity and viscosity increase rate over time) Regarding the viscosity of the coloring composition, on the day of preparation 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.). Furthermore, for a substance that has been left to stand at 40°C for 7 days from the day of preparation of the coloring composition, after the sample temperature is restored to 25°C, the time-dependent viscosity is measured according to the viscometry method described above, and the time-dependent viscosity is calculated according to the following formula Viscosity increase rate. Thickening rate over time = (viscosity over time)/(initial viscosity) × 100 (%)

(Evaluation of initial viscosity and viscosity increase rate over time) The dispersion stability was evaluated by the viscosity increase rate over time. The results are shown in Table 4. If the viscosity increase rate over time is more than 80% and less than 120%, it can be tolerated in practice. If the viscosity is reduced or increased beyond this range, when the coloring composition is coated on a glass substrate, the coating cannot be performed under the same coating conditions, resulting in productivity problems. More preferably, the range is between 90% and less than 110%. ○: The viscosity increase rate over time is more than 90% and less than 110% △: The viscosity increase rate over time is 80% or more and less than 90%, or 110% or more and less than 120% ×: The viscosity increase rate over time is less than 80%, or more than 120%

[Table 4] Table 4 coloring composition Dispersion stability evaluation Example 101 RP-1 △ Example 102 RP-2 △ Example 103 RP-3 △ Example 104 RP-4 △ Example 105 RP-5 △ Example 106 RP-6 〇 Example 107 RP-7 〇 Example 108 RP-8 〇 Example 109 RP-9 〇 Example 110 RP-10 〇 Example 111 RP-11 〇 Example 112 RP-12 〇 Example 113 RP-13 〇 Example 114 RP-14 〇 Example 115 RP-15 〇 Example 116 RP-16 〇 Example 117 RP-17 〇 Example 118 RP-18 〇 Example 119 RP-19 〇 Example 120 RP-20 〇 Example 121 RP-21 〇 Example 122 RP-22 △ Example 123 RP-23 △ Example 124 RP-24 △ Example 125 RP-25 〇 Example 126 RP-26 〇 Example 127 RP-27 〇 Example 128 RP-28 〇 Example 129 RP-29 〇 Example 130 RP-30 〇 Example 131 RP-31 〇 Example 132 RP-32 〇 Example 133 RP-33 〇 Example 134 RP-34 〇 Example 135 RP-35 〇 Example 136 RP-36 △ Example 137 RP-37 △ Example 138 RP-38 〇 Example 139 RP-39 〇 Example 140 RP-40 △ Example 141 RP-41 〇 Example 142 RP-42 〇 Example 143 RP-43 〇 Example 144 RP-44 〇 Example 145 RP-45 △ Example 146 RP-46 〇 Example 147 RP-47 △ Example 148 RP-48 〇 Comparative example 101 RP-49 〇 Comparative example 102 RP-50 × Comparative example 103 RP-51 ×

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

＜Manufacture of yellow coloring composition＞ (Preparation of coloring composition (YP-1)) The following mixture was stirred and mixed until it became uniform, and then an Eiger-mill (mini model M manufactured by Eiger Japan) was used using zirconia beads with a diameter of 0.5 mm. -250 MKII") was dispersed for 5 hours, and then filtered with a 5.0 μm filter to prepare a coloring composition (YP-1). C.I. Pigment Yellow 139 12.6 parts ("Cinilex(R) Yellow SY3C" manufactured by CINIC) Pigment Derivative C 1.4 parts Resin dispersant solution 1 12.0 parts Binder resin solution 1 6.0 parts Propylene glycol monomethyl ether acetate 68.0 parts

＜Manufacture of photosensitive coloring composition＞ [Example 201] (Preparation of photosensitive coloring composition (RR-1)) The following mixture was stirred and mixed until it was uniform, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (RR-1). In addition, regarding the colored composition (RP-1) and the colored composition (YP-1), the mixing ratio was adjusted so that when the transmittance of the coating film at 400 nm was 5%, the transmittance at 530 nm became 5%. Total of coloring composition (RP-1) and coloring composition (YP-1) 72. 86 copies Binder resin solution 1 1.40 parts Photopolymerizable monomer ("Aronix M-402" manufactured by Toagosei Co., Ltd.) 1.70 parts Photopolymerizable initiator ("IRGACURE OXE-02" manufactured by BASF) 0.17 parts Propylene glycol monomethyl ether acetate 23.87 parts

[Example 202 to Example 248, Comparative Example 201 to Comparative Example 203] (Preparation of photosensitive coloring compositions (RR-2 to RR-51)) The coloring composition (RP-1) was changed to the coloring composition described in Table 5, and the transmittance at 530 nm became 5% when the transmittance of the coating film at 400 nm was 5%. It was changed to the coloring composition (YP- Except for the mixing ratio of 1), photosensitive coloring compositions (RR-2 to RR-51) were produced in the same manner as in Example 201.

＜Evaluation of dispersion stability＞ The dispersion stability of the obtained photosensitive colored composition was measured in the same manner as the dispersion stability of the colored composition, and a three-stage evaluation was performed based on the following standards. ○: The viscosity increase rate over time is more than 95% and less than 105% △: The viscosity increase rate over time is 90% or more and less than 95%, or 105% or more and less than 110% ×: The viscosity increase rate over time is less than 90%, or more than 110%

<Evaluation of Coloring Strength> The obtained photosensitive coloring composition was spin-coated on a 6-inch glass wafer with a resist liquid for planarization film (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) , as pre-baking, use a hot plate at 100°C for 6 minutes. Furthermore, the coating film was cured by oven processing at 230° C. for 1 hour to form a 1.0 μm planarizing film, and a wafer with a planarizing film was obtained. Then, the obtained resist material was coated on the glass wafer with the planarization film using a spin coater, and as a prebaking, it was heated with a hot plate at 100° C. for 1 minute. Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.) was used to pass through a mask for forming 1.0 μm square pixels at a wavelength of 365 nm, with an exposure dose of 150 mJ/cm ² Make pattern exposure. Use an organic alkaline developer to develop the exposed coating for 1 minute. After liquid coating development, rinse with pure water using a 20-second rotary spray, and then pure water washing for 20 seconds. Afterwards, high-pressure air is used to blow away the water droplets remaining on the wafer, allowing the substrate to dry naturally to form a square pixel pattern. Thereafter, it was heated and dried at 230° C. for 20 minutes to prepare an evaluation substrate. During production, adjustments were made by changing the number of rotations of spin coating so that the transmittance at 530 nm became 5%. The coloring power of the coating film was evaluated in three stages based on the following criteria. ○: Film thickness is less than 0.55 μm △: 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 stages based on the following criteria. ○: Transmittance at 600 nm is over 90% △: The transmittance at 600 nm is more than 85% and less than 90% ×: The transmittance at 600 nm is less than 85%

Table 5 shows the photosensitive coloring composition evaluation results.

[table 5] table 5 Photosensitive coloring composition coloring composition Dispersion stability Tinting power transmittance Example 201 RR-1 RP-1 △ △ 〇 Example 202 RR-2 RP-2 △ △ 〇 Example 203 RR-3 RP-3 △ △ 〇 Example 204 RR-4 RP-4 △ △ 〇 Example 205 RR-5 RP-5 △ △ 〇 Example 206 RR-6 RP-6 〇 〇 〇 Example 207 RR-7 RP-7 〇 △ 〇 Example 208 RR-8 RP-8 〇 △ 〇 Example 209 RR-9 RP-9 〇 〇 〇 Example 210 RR-10 RP-10 〇 〇 〇 Example 211 RR-11 RP-11 〇 〇 〇 Example 212 RR-12 RP-12 〇 〇 〇 Example 213 RR-13 RP-13 〇 〇 〇 Example 214 RR-14 RP-14 〇 〇 〇 Example 215 RR-15 RP-15 〇 〇 〇 Example 216 RR-16 RP-16 〇 〇 〇 Example 217 RR-17 RP-17 〇 △ 〇 Example 218 RR-18 RP-18 〇 △ 〇 Example 219 RR-19 RP-19 〇 〇 〇 Example 220 RR-20 RP-20 〇 〇 〇 Example 221 RR-21 RP-21 〇 〇 〇 Example 222 RR-22 RP-22 △ △ △ Example 223 RR-23 RP-23 △ △ △ Example 224 RR-24 RP-24 △ △ △ Example 225 RR-25 RP-25 〇 △ △ Example 226 RR-26 RP-26 〇 △ △ Example 227 RR-27 RP-27 〇 〇 △ Example 228 RR-28 RP-28 〇 〇 △ Example 229 RR-29 RP-29 〇 〇 △ Example 230 RR-30 RP-30 〇 〇 △ Example 231 RR-31 RP-31 〇 〇 △ Example 232 RR-32 RP-32 〇 〇 △ Example 233 RR-33 RP-33 〇 〇 △ Example 234 RR-34 RP-34 〇 〇 △ Example 235 RR-35 RP-35 〇 〇 △ Example 236 RR-36 RP-36 △ △ △ Example 237 RR-37 RP-37 △ △ △ Example 238 RR-38 RP-38 〇 〇 △ Example 239 RR-39 RP-39 〇 〇 △ Example 240 RR-40 RP-40 △ △ △ Example 241 RR-41 RP-41 〇 〇 〇 Example 242 RR-42 RP-42 〇 〇 〇 Example 243 RR-43 RP-43 〇 〇 〇 Example 244 RR-44 RP-44 〇 〇 〇 Example 245 RR-45 RP-45 △ 〇 〇 Example 246 RR-46 RP-46 〇 〇 〇 Example 247 RR-47 RP-47 △ 〇 △ Example 248 RR-48 RP-48 〇 〇 〇 Comparative example 201 RR-49 RP-49 〇 × 〇 Comparative example 202 RR-50 RP-50 × 〇 × Comparative example 203 RR-51 RP-51 × 〇 ×

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

Furthermore, by using these photosensitive colored compositions, it is possible to provide color filters and sensors for image sensors that are thinner, have improved color resolution, and have improved color reproducibility.

without

without

Claims (9)

A diketopyrrolopyrrole pigment, characterized in that: represented by the following general formula (1), general formula (1) In the general formula (1), A ¹ and A ² each independently represent a five-membered ring or a six-membered ring that may have a substituent, and the atoms forming the ring are each independently a carbon atom, an oxygen atom, or a sulfur atom; R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a halogen atom. A diketopyrrolopyrrole pigment, characterized in that: represented by the following general formula (2), general formula (2) In the general formula (2), X ¹ to X ⁶ are independently -CR ⁵ R ⁶ -, -C(=O)-, -C(=S)-, an oxygen atom, or a sulfur atom; R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a halogen atom, and R ⁵ and R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent. group, or a phenyl group which may have a substituent. A pigment composition characterized by containing: the diketopyrrolopyrrole pigment as described in Claim 1 or Claim 2, and a pigment derivative. A colored composition characterized by containing: the diketopyrrolopyrrole pigment according to claim 1 or claim 2, or the pigment composition according to claim 3, and an organic solvent. The colored composition according to claim 4, further containing a photopolymerizable monomer and/or a photopolymerizable initiator. The colored composition according to Claim 4 or 5, wherein the moisture content in the colored composition is 0.1% by mass to 2.0% by mass relative to the entire colored composition. The colored composition according to Claim 4 or Claim 5, wherein the colored composition contains a metal component containing metal atoms selected from the group consisting of Li, Na, K, Cs, Mg, Ca, Fe, Cr, and Zr, and The total amount of the metal atoms in the metal component is 1 mass ppm to 1000 mass ppm relative to the entire coloring composition. A color filter having a film formed of the colored composition according to any one of claims 4 to 7 on a base material. A sensor having the color filter as described in claim 8.