TW202202576A - Pigment composition for color filters, coloring composition, color filter, liquid crystal display device and solid-state imaging element - Google Patents

Abstract

The purpose of the present invention is to provide: a pigment composition for color filters, said pigment composition having excellent storage stability and being capable of forming a pixel that has good brightness, contrast ratio, heat resistance, solvent resistance and dye transferability; a coloring composition; and a color filter which is formed using this pigment composition for color filters. The above are achieved by means of a pigment composition for color filters, said pigment composition containing a diketopyrrolopyrrole pigment represented by general formula (1) and a diketopyrrolopyrrole pigment represented by general formula (2), while being characterized in that the mass ratio of the pigment of general formula (1) to the pigment of general formula (2) is from 99.9:0.1 to 90.0:10.0.

Description

Pigment composition for color filter, coloring composition, color filter, liquid crystal display device, and solid-state imaging element

The present invention relates to a solid-state imaging element represented by a color liquid crystal display device, a complementary metal oxide semiconductor C-MOS (Complementary Metal Oxide Semiconductor, C-MOS), a charge coupled device (Charge Coupled Device, CCD), etc. , Coloring compositions of color filters used in organic electroluminescence (Electroluminescence, EL) display devices, electronic paper, etc., and filters including filter segments formed using the coloring compositions color filter.

On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is usually formed by evaporation or sputtering, and then an alignment for aligning the liquid crystal in a certain direction is formed on the transparent electrode. membrane. In order to fully obtain the performance of these transparent electrodes and alignment films, the forming step needs to be performed at a high temperature of generally 230° C. or higher, and heat resistance is required for color filters.

Contrast ratio and lightness are mentioned as important quality items requested|required for a color filter. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal will be disturbed, light will leak when it must block light (OFF state), and the transmitted light will be attenuated when it must transmit light (ON state), resulting in blurring. screen. Therefore, in order to realize a high-quality liquid crystal display device, it is indispensable to improve the contrast ratio. In addition, when a color filter with low lightness is used, the transmittance of light is low, and thus a dark screen is produced. In order to obtain a bright screen, it is necessary to increase the number of backlights serving as light sources. However, from the viewpoint of suppressing power consumption, there is a trend toward higher brightness of color filters.

As colorants for forming the red filter segment, C.I. Pigment Red 254, C.I. Pigment Red 291, C.I. Pigment Red 242, and C.I. Pigment Red 177 are generally widely used. CI Pigment Red 254 and CI Pigment Red 291, which are diketopyrrolopyrrole pigments, are pigments particularly excellent in lightness. However, in recent years, there is a strong desire for high contrast in color filters. The primary particle diameter of the ketopyrrolopyrrole-based pigment is made as fine as possible. However, the micronized diketopyrrolopyrrole-based pigment has the property of being easy to crystallize due to its intermolecular hydrogen bond, so there is a problem in that crystallization is caused in the heating step at the time of forming the color filter, which may cause crystallization. produce foreign bodies.

In Patent Document 1, it is disclosed that by using CI Pigment Red 291 in combination with a diketopyrrolopyrrole pigment of a specific structure, the precipitation of crystallization in the heating step can be suppressed, but the brightness, contrast ratio, heat resistance, and solvent resistance. Further improvements are required. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-155232

[The problem to be solved by the invention] An object of the present invention is to provide a pigment composition for color filters, a coloring composition using the same, which are excellent in storage stability and can form pixels having good brightness, contrast ratio, heat resistance, solvent resistance, and dye migration. A color filter formed of a colored composition. [Means of Solving Problems]

The inventors of the present invention have made diligent studies and, as a result, found that the above problems can be solved by a pigment composition containing two kinds of diketopyrrolopyrrole pigments having different structures in a specific mass ratio, and completed the present invention.

[通式（1）中，X表示鹵素原子] 通式（2） [化2]

[通式（2）中，Y及Z分別獨立地為氫原子、鹵素原子、氰基、碳數1～20的可具有取代基的烷基、可具有取代基的苯基；其中，Y及Z的至少一個為碳數3～18的烷基]That is, the present invention relates to a pigment composition for a color filter comprising a diketopyrrolopyrrole pigment represented by the general formula (1) and a diketopyrrolopyrrole pigment represented by the general formula (2). , and the mass ratio of the general formula (1) and the general formula (2) is 99.9:0.1 to 90.0:10.0. General formula (1) [Chemical 1]

[In general formula (1), X represents a halogen atom] General formula (2) [Chemical 2]

[In the general formula (2), Y and Z are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted phenyl group; wherein, Y and At least one of Z is an alkyl group having 3 to 18 carbon atoms]

In addition, the present invention relates to the pigment composition for color filters, which further contains a pigment derivative.

Moreover, this invention relates to the coloring composition for color filters containing a colorant, a resin, and a solvent, and the coloring agent contains the said pigment composition for color filters.

Moreover, this invention relates to the said coloring composition for color filters, which further contains a photopolymerizable monomer and/or a photopolymerization initiator.

In addition, the present invention relates to a color filter including a filter segment formed of the coloring composition for a color filter.

In addition, the present invention relates to a liquid crystal display device including the color filter.

In addition, the present invention relates to a solid-state imaging element including the color filter. [Effect of invention]

According to the present invention, it is possible to provide a pigment composition for a color filter, a coloring composition, and a coloring composition using the same, which are excellent in storage stability and can form pixels having good brightness, contrast ratio, heat resistance, solvent resistance, and dye migration properties. A color filter formed of a colored composition.

Hereinafter, each component constituting the pigment composition for color filters and the coloring composition for color filters of the present invention will be described in detail. In addition, "C.I." in this application refers to a dye index (Colour Index, C.I.). Furthermore, in the expression "(meth)acryloyl group", "(meth)acrylic acid group", "(meth)acrylic acid", "(meth)acrylate" and "(meth)acryloyloxy In the case of "base", unless otherwise specified, "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic and/or methacrylic", "acrylate and/or methacrylate" and "acryloyloxy and/or methacryloyloxy".

<Pigment composition for color filters> The pigment composition for color filters of the present invention contains the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2) in a mass ratio of 99.9:0.1 to 90.0:10.0. It has the effect of being excellent in brightness, contrast ratio, heat resistance, solvent resistance and dye migration.

(Diketopyrrolopyrrole Pigment (A1) of General Formula (1)) The diketopyrrolopyrrole pigment (A1) represented by the general formula (1), which is an essential component of the pigment composition of the present invention, will be described.

[通式（1）中，X表示鹵素原子]General formula (1) [Chemical 3]

[In the general formula (1), X represents a halogen atom]

In X, fluorine, bromine, chlorine, and iodine are mentioned as "halogen atom", and chlorine and bromine are preferable from the viewpoint of the lightness and contrast ratio. Specific examples of the diketopyrrolopyrrole pigment of the general formula (1) usable in the present invention include C.I. Pigment Red 254 and 291, but are not limited to these. From the viewpoint of lightness, C.I. Pigment Red 291 is preferable.

(Diketopyrrolopyrrole Pigment (A2) of General Formula (2)) The diketopyrrolopyrrole pigment (A2) represented by the general formula (2), which is an essential component of the pigment composition of the present invention, will be described.

[通式（2）中，Y及Z分別獨立地為氫原子、鹵素原子、氰基、碳數1～20的可具有取代基的烷基、可具有取代基的苯基；其中，Y及Z的至少一個為碳數3～18的烷基]General formula (2) [Chemical 4]

[In the general formula (2), Y and Z are each independently a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, and an optionally substituted phenyl group; wherein, Y and At least one of Z is an alkyl group having 3 to 18 carbon atoms]

In Y and Z, fluorine, bromine, chlorine, and iodine are mentioned as "halogen atom".

In Y and Z, as "the alkyl group having 1 to 20 carbon atoms which may have a substituent", there are unsubstituted or ether-bonded oxyalkylene groups, etc., which may be linear or branched, Specifically, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl , octadecyl, eicosyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl group, 3-ethoxypropyl group, polyoxyethylene group, etc., but not limited to these.

In Y and Z, as the "phenyl group which may have a substituent", an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, and a sulfamoyl group can be mentioned. A phenyl group having a substituent such as a sulfamoyl group and an alkoxy group having 1 to 4 carbon atoms. More specifically, phenyl, p-methylphenyl, 4-tert-butylphenyl, p-nitrophenyl, p-methoxyphenyl, p-chlorophenyl, 2,4-dichlorobenzene can be mentioned group, 3-aminocarboxyphenyl, etc., but are not limited to these.

At least one of Y and Z is "an alkyl group having 3 to 18 carbon atoms". Examples of the "alkyl group having 3 to 18 carbon atoms" include propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl Alkyl, octadecyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, cyclohexyl, isobornyl, etc., but not limited to these. The number of carbon atoms in the alkyl group is preferably from 4 to 12 carbon atoms, and more preferably from 4 to 8 carbon atoms, from the viewpoints of heat resistance (crystallization during processing), contrast ratio, and solvent resistance. When the length of the alkyl group is long, the heat-induced aggregation of the diketopyrrolopyrrole pigment of the general formula (1) can be suppressed due to the steric hindrance effect, and the contrast ratio and the heat resistance become favorable. On the other hand, when the alkyl group is too long, the dispersion stability is deteriorated and the solubility in the solvent is improved, so that the solvent resistance and the dye migration property tend to be deteriorated.

Specific examples of the diketopyrrolopyrrole pigments of the general formula (2) that can be used in the present invention are listed below, but are not limited to these.

[hua 5]

In the present invention, the content of the diketopyrrolopyrrole pigment represented by the general formula (2) is 0.1 based on the total mass of the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2). The range of mass % - 10 mass %. The range of 0.1 mass % - 5.0 mass % is preferable, and the range of 0.1 mass % - 3.0 mass % is more preferable.

When the ratio of the diketopyrrolopyrrole pigment of the general formula (2) exceeds 10 mass %, the effect of improving heat resistance (crystallization inhibition) is obtained, but the diketopyrrolopyrrole pigment of the general formula (1) is impaired excellent brightness and poor storage stability or solvent resistance. On the other hand, if the ratio of the diketopyrrolopyrrole pigment represented by the general formula (2) is less than 0.1 mass %, the enhancement of contrast and the heat resistance (suppression of crystallization) are insufficient. When the effect of suppressing crystallization is not sufficient, light scattering is caused by the crystalline foreign matter deposited on the surface of the coating film in the heating step, thereby causing a decrease in brightness and contrast ratio. Therefore, by using the coloring composition containing the diketopyrrolopyrrole pigment of the general formula (2) at the above ratio, high brightness and high contrast ratio can be achieved, and the general formula (1) can be suppressed even by the heating step. crystallization of the diketopyrrolopyrrole pigment.

(Manufacturing method of diketopyrrolopyrrole pigment) The diketopyrrolopyrrole pigment represented by the general formula (1) or the general formula (2) can be produced by a succinic acid diester synthesis method. That is, 1 mol of succinic acid diester and 2 mol of any benzonitrile compound of the following general formula (50) or general formula (60) are dissolved in an inert organic solvent such as tert-amyl alcohol, in a base In the presence of a metal or an alkali metal alkoxide, a condensation reaction is performed at a high temperature of 80°C to 110°C to generate an alkali metal salt of a diketopyrrolopyrrole compound, and then, an alkali metal salt of the diketopyrrolopyrrole compound is produced. The diketopyrrolopyrrole pigment of the general formula (1) or the general formula (2) can be obtained by protonating the salt with water, alcohol, acid, or the like. At this time, the size of the obtained primary particle diameter can be controlled by the temperature during protonation, the type, ratio or amount of water, alcohol or acid. The method for producing the diketopyrrolopyrrole pigment represented by the general formula (1) or the general formula (2) is not limited to this method.

[通式（50）中，X表示鹵素原子]General formula (50) [Chemical 6]

[In the general formula (50), X represents a halogen atom]

[通式（60）中，Y及Z分別獨立地為氫原子、鹵素原子、氰基、可具有取代基的烷基、可具有取代基的苯基；其中，Y及Z的至少一個為碳數3～18的可具有取代基的烷基]General formula (60) [Chemical 7]

[In the general formula (60), Y and Z are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, a phenyl group which may have a substituent; wherein, at least one of Y and Z is a carbon Alkyl groups which may have substituents from 3 to 18]

(other colorants) The pigment composition and coloring composition of the present invention may be arbitrarily selected and used in combination with various conventionally known pigments and dyes in addition to the essential components of the diketopyrrolopyrrole pigment represented by the general formula (1) and the general formula (2). Contains in the form of a colorant. Hereinafter, typical pigments and dyes that can be used in the present invention are listed.

Examples of red pigments that can be used in the present invention include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48 : 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88 , 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187 , 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 255, 264, 270, 272, 273, 274, 276, 277, 278 , 279, 280, 281, 282, 283, 284, 285, 286, 287, 295, 296, etc., but are not particularly limited to these. In addition, red dyes such as xanthene-based, cyanine-based, azo-based, and anthraquinone-based dyes can also be used. Specifically, salt-forming compounds of xanthene-based acid dyes such as C.I. acid red 52, 87, 92, 289, and 338 can be mentioned.

Examples of orange pigments that can be used in the present invention include C.I. pigment orange 38, 43, or 71, but are not particularly limited to these.

Examples of yellow pigments that can be used in the present invention include CI pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,213,214,218,219,220,221,231,233 or The quinophthalone-based pigments and the like described in Japanese Patent No. 4993026 are not particularly limited to these. In addition, yellow dyes such as quinoline-based, azo-based, methine-based, coumarin-based, and isoindoline-based dyes can also be used.

Examples of green pigments that can be used in the present invention include CI pigment green (pigment green) 7, 10, 36, 37, 58, 59, 62, 63, Japanese Patent Laid-Open No. 2008-19383, and Japanese Patent Laid-Open No. 2007- Zinc phthalocyanine pigments described in Gazette 320986, Japanese Patent Laid-Open No. 2004-70342, International Publication No. 2015/118720 Handbook, etc., aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, etc., but not Especially limited to these. In addition, green dyes such as triarylmethane-based, phthalocyanine-based, and squaraine-based dyes can also be used.

Examples of blue pigments usable in the present invention include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6 , 16, 22, 60, 64, the aluminum phthalocyanine pigments described in Japanese Patent Laid-Open No. 2004-333817, Japanese Patent No. 4893859, etc., but are not particularly limited to these.

Examples of violet pigments that can be used in the present invention include CI 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., but are not particularly limited to these.

Metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silicon dioxide, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, etc. can also be used in the pigment composition of the present invention. Inorganic pigments such as carbon black.

When the pigment composition of the present invention and other colorants are used in combination, a red pigment or a yellow pigment is often used in combination in terms of the relationship with the color characteristics. Specifically, as the red pigment to be combined, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 269, and C.I. Pigment Red 296 are preferable from the viewpoint of color characteristics. The yellow pigments are preferably C.I. Pigment Yellow 138 or the quinophthalone-based pigments described in Japanese Patent No. 4993026, C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 150 from the viewpoint of color properties.

＜Pigment Derivatives＞ The pigment composition or coloring composition of the present invention may contain a pigment derivative for the purpose of suppressing the growth of pigment crystals and improving the dispersibility of the pigment. As the dye derivative usable in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue can be used. For example, compounds having acidic functional groups such as sulfo groups, carboxyl groups, and phosphoric acid groups, and amine salts thereof, compounds having sulfonamido groups or basic functional groups such as tertiary amine groups at the terminals, compounds having phenyl groups or Compounds with neutral functional groups such as phthalimide alkyl groups. Examples of organic dyes include diketopyrrolopyrrole-based pigments; phthalocyanines such as copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, and metal-free phthalocyanine Cyanine pigments; anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, xanthrone, anthraquinone, indanthrone, picanthrone, violanthrone, etc.; quinacridine Peridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thiazine indigo pigments; Triazine pigments; Benzimidazolone pigments; Indoles such as benzisoindole pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; naphthol pigments; reduction (threne) pigments; metal complex pigments; azo, disazo, Azo pigments such as polyazo etc. More specifically, Japanese Patent Laid-Open No. 61-246261, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. Hei 09-272812, Japanese Patent Laid-Open No. 10-245501, Japanese Patent Laid-Open No. Hei 09-272812, Japanese Patent Laid-Open No. 10-265697, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2001-172520, Japanese Patent Laid-Open No. 2001-220520, Japanese Patent Laid-Open No. 2002-201377, Japanese Patent Laid-Open No. 2001-201377 Japanese Patent Laid-Open No. 2003-165922, Japanese Patent Laid-Open No. 2003-168208, Japanese Patent Laid-Open No. 2003-171594, Japanese Patent Laid-Open No. 2004-217842, Japanese Patent Laid-Open No. 2005-213404, Japanese Patent Laid-Open No. 2003-171594 Japanese Patent Laid-Open No. 2006-291194, Japanese Patent Laid-Open No. 2007-079094, Japanese Patent Laid-Open No. 2007-226161, Japanese Patent Laid-Open No. 2007-314681, Japanese Patent Laid-Open No. 2007-314785, Japanese Patent Laid-Open No. 2007-314785 Patent Laid-Open No. 2008-31281, Japanese Patent Laid-Open No. 2009-57478, Handbook No. WO2009/025325, Handbook No. WO2009/081930, Japanese Patent Laid-Open No. 2011-162662, Handbook No. WO2011/052617, Japanese Patent Laid-Open No. 2011-162617 Laid-open Publication No. 2012-172092, Japanese Patent Laid-Open No. 2012-208329, Japanese Patent Laid-Open No. 2012-226110, Handbook WO2012/102399, Japanese Patent Laid-Open No. 2014-5439, Handbook WO2016/163351, Japanese Known dye derivatives described in Japanese Patent Laid-Open No. 2017-156397, Japanese Patent No. 5753266 and the like can be used alone or in combination of two or more. In addition, in these documents, there are cases in which the dye derivatives are described as derivatives, pigment derivatives, pigment dispersants, or only compounds, but the organic dye residues are described as having an acidic group, a basicity, and the like. A compound of a functional group such as a group or a neutral group has the same meaning as a dye derivative.

When a dye derivative is used in the present invention, a dye derivative having a basic substituent is preferred in that the effect of suppressing aggregation of pigments is remarkable. Furthermore, from the viewpoint of hue or contrast ratio, the organic dye residue is preferably derived from a diketopyrrolopyrrole-based pigment, an anthraquinone-based pigment, a thiazine-indigo-based pigment, a quinophthalone-based pigment, or a diketopyrrolopyrrole-based pigment. Nitrogen pigments.

＜Miniaturization of pigments＞ When the coloring agent used for the coloring composition of this invention is a pigment, it is preferable to refine|miniaturize and use it. The miniaturization method is not particularly limited, and for example, any of wet milling, dry milling, and dissolution and precipitation methods can be used, and salt milling can be performed by a kneader method, which is a type of wet milling, as exemplified in the present invention. (salt milling) processing, etc. to be refined. The average primary particle diameter of the pigment determined by a transmission electron microscope (TEM) is preferably in the range of 5 nm to 90 nm. When it is less than 5 nm, it is difficult to disperse in an organic solvent, and when it exceeds 90 nm, a sufficient contrast ratio cannot be obtained. For this reason, the more preferable average primary particle diameter is in the range of 10 nm to 70 nm.

The so-called salt mill treatment is treatment using a kneader, two-rod roll mill, three-rod roll mill, ball mill, attritor, sand Batch or continuous kneaders such as mills, planetary mixers, etc., mechanically knead the mixture of pigments, water-soluble inorganic salts and water-soluble organic solvents while heating, and then remove water-soluble inorganic salts by washing with water with water-soluble organic solvents. The water-soluble inorganic salt acts as a crushing aid, and at the time of salt milling, the pigment is crushed by utilizing the hardness of the inorganic salt. By optimizing the conditions when the pigment is subjected to salt milling, a pigment having a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution can be obtained.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, and it is preferable to use sodium chloride (table salt) in terms of price. In terms of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, relative to 100 parts by mass of the pigment.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is an organic solvent that dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. Among them, since the temperature rises during the salt milling and the solvent is easily evaporated, a high-boiling solvent having 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, and the like. The water-soluble organic solvent is preferably used in 5 parts by mass to 1000 parts by mass, and most preferably in the range of 50 parts by mass to 500 parts by mass, relative to 100 parts by mass of the pigment.

When performing the salt mill treatment, in order to improve the kneading efficiency, a dye derivative may be used in combination. It is very effective for miniaturization and sizing of pigments. In the miniaturization of the diketopyrrolopyrrole-based pigment composition used in the present invention, the dye derivatives are preferably used, but are not limited to these. It is preferable that the usage-amount of a pigment derivative is an extent which does not affect a color tone, ie, the range of 0.5 mass % - 30 mass % with respect to 100 mass % of pigments.

In addition, when salt milling is performed, resin may be added as needed. The type of resin to be used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin to be used is preferably solid at room temperature and water-insoluble, and is further preferably partially soluble in the organic solvent. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

<Coloring composition for color filter> The coloring composition for color filters of the present invention contains at least a colorant, a resin, and a solvent containing the pigment composition for color filters of the present invention. In addition, a resin-type dispersant, a photopolymerizable monomer for imparting photosensitivity, a photopolymerization initiator, or the like can be used as necessary.

<Resin type dispersant> The coloring composition of the present invention may use a resin-type dispersant in combination. The dispersant includes a colorant-affinity site having the property of being adsorbed to the added colorant or a colorant derivative, and a site having compatibility with the colorant carrier, and exerts adsorption to the added colorant to disperse in the colorant carrier stabilizing effect. As the resin-type dispersant, specifically, polycarboxylates such as polyurethane and polyacrylate; unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acids can be used Ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyamidoamine phosphates, hydroxyl-containing polycarboxylates or modifications of these; by poly(lower alkylene imines) ) and oily dispersants such as amides or their salts formed by the reaction of polyesters with free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, 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. may be used alone or in combination of two or more, but are not necessarily limited to these.

Among the resin-type dispersants, a graft copolymer containing a nitrogen atom is well known for the reason that the viscosity of the dispersion becomes low and the contrast ratio is high when added in a small amount; amine groups, quaternary ammonium bases, nitrogen-containing acrylic block copolymers containing functional groups such as nitrogen-containing heterocycles, and urethane-based polymer dispersants.

When a resin-type dispersant is used in combination in the present invention, it is preferably a resin-type dispersant having an acidic substituent, and among them, a resin-type dispersant having an aromatic carboxyl group or a phosphoric acid group prevents the re-dispersion of the colorant after dispersing. The effect of agglomeration is particularly large, so it is particularly good. Examples of the resin-type dispersant having an aromatic carboxyl group include WO2008/007776 A, JP 2008-029901 A, JP 2009-155406 A, JP 2009-155406 A, JP 2009-155406 A The resin-based dispersants described in Japanese Patent Laid-Open No. 2010-185934 and Japanese Patent Laid-Open No. 2011-157416 are not limited to these.

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

＜Resin＞ The resin which is an essential component of the coloring composition of this invention disperse|distributes, dyes, or permeates a colorant, and thermoplastic resin etc. are mentioned. Moreover, when using in the form of an alkali-developable coloring resist material, it is preferable to use the alkali-soluble vinyl-type resin which copolymerized the ethylenically unsaturated monomer containing an acidic group. In addition, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used in an alkali-developable colored resist material, when a coating film is formed by exposure with an active energy ray, the resin develops The three-dimensional crosslinking, whereby the colorant is fixed, the heat resistance becomes good, and the discoloration (deterioration of the spectroscopic properties) of the colorant due to heat can be suppressed. Moreover, it also has the effect of suppressing aggregation and precipitation of a colorant component also in a developing process.

The resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in all wavelength regions of 400 nm to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the resin is preferably in the range of 2,000 to 80,000, and more preferably in the range of 3,000 to 40,000, in order to properly disperse the colorant. In addition, the number average molecular weight (Mn) is preferably in the range of 3,000 to 40,000, and the value of Mw/Mn is preferably 10 or less.

When the resin is used as a photosensitive coloring composition for color filters, the carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, and an affinity group for the colorant carrier and solvent The balance of the acting aliphatic groups and aromatic groups is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 mgKOH/g to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility with respect to the developing solution may be poor and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH/g, there is a case where a fine pattern is not left.

The resin is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant in terms of good film-forming properties and various resistances. In terms of color characteristics, it is preferably used in an amount of 1,000 parts by mass or less.

Examples of thermoplastic resins used for resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate. Copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, fiber Polyethylene (High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE)), polybutadiene and polyimide resin, etc. Among them, an acrylic resin is preferably used.

Examples of vinyl-based alkali-soluble resins obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having acidic groups such as carboxyl groups and sulfo groups. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, and an ethylene/(meth)acrylic acid copolymer. compound or isobutylene/maleic acid (anhydride) copolymer, etc. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, can be suitably used because of its high heat resistance and transparency.

As an active energy ray curable resin which has an ethylenically unsaturated double bond, the resin into which an unsaturated ethylenic double bond was introduce|transduced by the method of (i) or (ii) shown below is mentioned, for example.

[Method (i)] As the method (i), there is, for example, a method of adding an epoxy group to a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other monomers. The carboxyl group of the unsaturated monobasic acid which has an unsaturated ethylenic double bond is reacted, and the produced hydroxyl group is made to react with a polybasic acid anhydride, and an unsaturated ethylenic double bond and a carboxyl group are introduced.

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

Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, α-halogenated alkyl group of (meth)acrylic acid, and alkoxy group. , a halogen, a nitro group, a monocarboxylic acid such as a cyano substituent, and the like, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like, and these may be used alone or in combination of two or more. The number of carboxyl groups and the like may be increased, and the remaining anhydride groups may be hydrolyzed using tricarboxylic anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride as necessary. In addition, as the polybasic acid anhydride, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used, the unsaturated ethylenic double bond can be further increased.

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

[Method (ii)] As the method (ii), there is a method in which an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group is used, and an unsaturated ethylenic monomer having a hydroxyl group is used in combination with another unsaturated monobasic acid having a carboxyl group. The side chain hydroxyl groups of the copolymers obtained by copolymerizing the monomers or other monomers are reacted.

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

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, and the like. It is not limited to these, You may use 2 or more types together.

<Thermosetting compound> The coloring composition of this invention may contain a thermosetting compound. Examples of the thermosetting compound include epoxy compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, and rosin-modified fumaric acid compounds and/or resins. , melamine compound and/or resin, urea compound and/or resin, phenol compound and/or resin, but the present invention is not limited thereto. In the case where a thermosetting compound is used in the present invention, an epoxy compound is preferred from the viewpoints of heat resistance, solvent resistance, and the like. The epoxy compound is not particularly limited as long as it has an epoxy group, and may be a low molecular weight compound or a high molecular weight compound such as a resin. In order to obtain a coating film with a high crosslink density, a polyfunctional one is particularly preferred. epoxy compound.

As a preferable weight average molecular weight of an epoxy compound, 200 or more and 100,000 or less are preferable. A more preferable molecular weight is 300 or more and 10,000 or less, and still more preferably 500 or more and 5000 or less.

As an epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a cresol novolak type epoxy compound, a biphenyl type epoxy compound, an alicyclic epoxy compound, etc. can be used. Preferred are novolak-type epoxy compounds and alicyclic epoxy compounds, and particularly preferred are alicyclic epoxy compounds. The number of functional groups is preferably difunctional or more, and more preferably trifunctional or more, in terms of excellent thermal crosslinkability.

Examples of the bifunctional epoxy compound include EPICLON 830, 840, 850, 860, 1050, 2050, 3050, 4050, 7050, HM-091, 101 manufactured by DIC; Nagase Kasei Denacol EX-211, 212, 252, 711, 721, etc. manufactured by Nagase ChemteX.

Examples of the trifunctional or higher polyfunctional epoxy compound include a novolak-type epoxy compound and EHPE3150 (manufactured by Daicel Chemical Industry Co., Ltd.) which is a polymer alicyclic main chain epoxy compound. Specific examples of the novolak-type epoxy compound include EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-4500, EOCN-4600, XD-1000, XD-1000-L, XD -1000-2L, NC-3000, NC-3000-H (the above are manufactured by Nippon Kayaku Co., Ltd.); YDPN-638, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700- 7. YDCN-700-10, YDCN-704, YDCN-704A (the above are manufactured by Nippon Steel Chemical Co., Ltd.); N-660, N-665, N-670, N-673, N-680, N-690, N-695, N-665-EXP, N-672-EXP, N-655-EXP-S, N-662-EXP-S (the above are manufactured by DIC), etc. In addition, Techmore VG3101 (manufactured by Printec) as a trifunctional epoxy compound, TETRAD-C as a tetrafunctional epoxy compound, Tate Rad (TETRAD)-X (the above is manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc. In addition, Denacol EX-313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, etc. made by Nagase ChemteX can also be mentioned. Moreover, JER1031S, 1302H60, 604, 630, 630LSD etc. by Mitsubishi Chemical Corporation can also be mentioned.

＜Organic solvent＞ The coloring composition of the present invention contains an organic solvent in order to facilitate the operation of sufficiently dispersing the coloring agent in the coloring agent carrier, and making a dry film thickness of 0.2 μm to 0.2 μm on a substrate such as a glass substrate. 5 μm was applied to form a colored film. In addition to considering the good coatability of the coloring composition, the organic solvent is selected in consideration of the solubility and safety of each component of the coloring composition.

As an organic solvent, ethyl lactate, benzyl alcohol, 1,3-butanediol (1,3-butanediol), 1,3-butanediol (1,3-butylene glycol), 1,3- Butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1- Ketone, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1 -Butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diol Ethylbenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, 2-butylbenzene, 3-butylbenzene, γ-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Alcohol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol Acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glycerin 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, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isoamyl acetate Butyl ester, propyl acetate, dibasic acid ester, etc. These solvents can be used alone, or two or more of them can be mixed and used in an arbitrary ratio as necessary.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol are preferably used in terms of good dispersibility and permeability of the colorant, and good coatability of the coloring composition. Ethylene glycol acetates such as alcohol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol, diacetone alcohol, 3-methoxybutanol, propylene glycol monomethyl ether, etc., or cyclohexanone ketones.

In addition, the organic solvent is preferably 500 parts by mass to 100 parts by mass with respect to 100 parts by mass of the coloring agent, since the coloring composition can be adjusted to an appropriate viscosity and a coloring film having a desired uniform film thickness can be formed. It was used in an amount of 4000 parts by mass.

<Photopolymerizable monomer> The coloring composition of this invention may contain a photopolymerizable monomer. The photopolymerizable monomer includes a monomer or an oligomer that is hardened by ultraviolet rays, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays, heat, etc. to form transparent resins include methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanedi Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylates, Pentaerythritol Tetra(meth)acrylate, 1,6-Hexanediol Diglycidyl Ether Di(meth)acrylate, Bisphenol A Diglycidyl Ether Di(meth)acrylate, Neopentyl Glycol Diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecyl(meth)acrylate, ester acrylate, methylol Various acrylates such as (meth)acrylates, epoxy (meth)acrylates, and urethane acrylates of alkylated melamine, and methacrylates, (meth)acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. , but not necessarily limited to these. One of these photopolymerizable monomers may be used alone, or two or more of them may be mixed and used in an arbitrary ratio as necessary.

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

<Photopolymerization initiator> The coloring composition of the present invention may contain a photopolymerization initiator in order to harden the composition by ultraviolet irradiation and to form filter segments by photolithography. Moreover, it can prepare in the form of a solvent developing type or an alkali developing type photosensitive coloring composition.

As a photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl) can be used Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Propane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone compounds such as butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin-based compounds such as benzoin isopropyl ether or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxydiphenyl ketone, acrylated benzophenone, 4-benzyl-4'-methyldiphenyl sulfide or 3,3',4,4'-tetrakis(tert-butylcarbonylperoxide)diphenyl Benzophenone-based compounds such as ketone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Thioxanthone-based compounds such as anthrone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl) )-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl) base)-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-yl)-4,6-bis( trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine or 2,4-trichloromethyl-(4'-methoxystyryl)- Triazine compounds such as 6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzyl oxime)] or O-(acetyl) -N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl) ethylene) oxime ester compounds such as hydroxylamine; bis(2,4,6-trimethylbenzene) Phosphine compounds such as carboxyl)phenylphosphine oxide or 2,4,6-trimethylbenzyldiphenylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone and other quinones borate-based compound; carbazole-based compound; imidazole-based compound; or titanocene-based compound and the like. One of these photopolymerization initiators may be used alone, or two or more of them may be mixed and used in an arbitrary ratio as necessary.

The content of the photopolymerization initiator is preferably 2 parts by mass to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 parts by mass to 150 parts by mass from the viewpoint of photocurability and developability.

＜Sensitizer＞ Furthermore, a sensitizer may be contained in the coloring composition of this invention. Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives, dibenzalacetone, and the like, and 1,2-diketones represented by benzalkonium and camphorquinone. Derivatives, Benzoin Derivatives, Fluorene Derivatives, Naphthoquinone Derivatives, Anthraquinone Derivatives, Xanthene Derivatives, Thixanthene Derivatives, Xanthone Derivatives, Thixanthone Derivatives, Coumarin Derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxa Azine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squaraine derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetraphenyl Porphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalinoporphyrazine derivatives, naphthalocyanine derivatives, Subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, sulfur Spiropyran derivatives, metal arene complexes, organoruthenium complexes or Michler's ketone derivatives, biimidazole derivatives, α-oxoesters, acylphosphine oxides, benzoic acid Methyl phenyl glyoxylate, 9,10-phenanthrenequinone, ethylanthraquinone, 4,4'-diethyl isophthalophenone, 3,3'-tetrakis(4,4'-diethyl isophthalophenone) tertiary butyl carbonyl peroxide) benzophenone or 4,4'-tetrakis (tertiary butyl carbonyl peroxide) benzophenone, 4,4'-diethylamino benzophenone and the like. These sensitizers may be used alone, or two or more of them may be mixed and used in any ratio as necessary.

More specifically, "Handbook of Pigments" edited by Nobu Ogawara et al. (1986, Kodan Co., Ltd.), "Chemistry of Functional Pigments" edited by Nobu Ogawara et al. The sensitizers are described in "Special Functional Materials" (1986, CMC) edited by Man, but are not limited to these. Moreover, you may contain the sensitizer which shows absorption with respect to the light of an ultraviolet-to-near-infrared region in addition.

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

<thiol compound> The coloring composition of this invention may contain the thiol compound which functions as a chain transfer agent. As the thiol compound, a polyfunctional thiol compound having two or more thiol groups is preferable, and examples thereof include hexanedithiol, decanedithiol, and 1,4-butanediol dithiopropane. acid ester, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithioglycolate Methylolpropane trithiopropionate, Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetrathioglycolate, Pentaerythritol tetrathiopropionate, Tris(2-mercaptopropionate) Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6 - dimercapto-s-triazine etc. One of these polyfunctional thiol compounds may be used alone, or two or more of them may be mixed and used in an arbitrary ratio as necessary.

The content of the thiol compound is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the mass of the total solid content of the coloring composition for a color filter (100% by mass). If the content of the thiol compound is less than 0.1 mass %, the effect of adding the thiol compound will be insufficient, and if it exceeds 30 mass %, the sensitivity may be too high and the resolution may be lowered on the contrary.

＜Antioxidants＞ The coloring composition of this invention may contain antioxidant. Antioxidants prevent photopolymerization initiators or thermosetting compounds contained in the coloring composition from being oxidized and yellowed due to thermal hardening or thermal steps during indium tin oxide (ITO) annealing, thereby improving the coating film. transmittance. Therefore, by containing an antioxidant, yellowing by oxidation at the time of a heating process can be prevented, and the transmittance|permeability of a high coating film can be obtained.

The "antioxidant" in the present invention may be any compound as long as it has an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. Specifically, examples of the antioxidant include hindered phenol-based, hindered amine-based, As the phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, known ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, from the viewpoint of both the transmittance and sensitivity of the coating film, preferable antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, or sulfur-based antioxidants. Antioxidants. In addition, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant is more preferred.

One of these antioxidants may be used alone, or two or more of them may be mixed and used in an arbitrary ratio as necessary.

When content of antioxidant is 0.1 mass % - 5.0 mass % based on the solid content mass of the coloring composition for color filters (100 mass %), since brightness and sensitivity are favorable, it is more preferable.

<Amine compound> In addition, the coloring composition of the present invention may contain an amine compound having an action of reducing dissolved oxygen. As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate and N,N-dimethyl-p-toluidine, etc. .

＜Leveler＞ In order to improve the leveling property of the composition on the transparent substrate, a leveling agent may be added to the coloring composition of the present invention. As a leveling agent, the dimethylsiloxane which has a polyether structure or a polyester structure in a main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-2122 manufactured by BYK-Chemie 333 et al. As a specific example of the dimethylsiloxane which has a polyester structure in a main chain, BYK-310, BYK-370, etc. by BYK-Chemie are mentioned. It can also be used in combination with dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain. The content of the leveling agent is usually preferably 0.003 to 0.5 mass % based on the total mass of the coloring composition (100 mass %).

A particularly preferred leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and it is useful because it contains a hydrophilic group but has low solubility in water, and is useful for adding to coloring In the case of the composition, it has the characteristics of low surface tension reducing ability, and even if the surface tension reducing ability is low, the leveling agent with good wettability to the glass plate can be preferably used because it does not cause problems. A leveling agent that sufficiently suppresses the chargeability at the addition amount of coating film defects due to bubbles. As a leveling agent which has such preferable characteristics, the dimethyl polysiloxane which has a polyalkylene oxide unit can be used suitably. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit to the dimethylpolysiloxane may be a pendant type, a bond in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane. Either of the terminal-modified type bonded to the terminal of dimethylpolysiloxane, and the linear block copolymer type bonded alternately and repeatedly with dimethylpolysiloxane. Dimethyl polysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, but not limited to these.

Anionic, cationic, nonionic or amphoteric surfactants can also be added to the leveling agent. Two or more types of surfactants may be used in combination. Examples of the anionic surfactant to be added to the leveling agent auxiliary include: polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, alkylnaphthalene Sodium Sulfonate, Sodium Alkyl Diphenyl Ether Disulfonate, Monoethanolamine Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Ammonium Lauryl Sulfate, Monoethanolamine Stearate, Sodium Stearate, Sodium Lauryl Sulfate, Styrene - Monoethanolamine of acrylic copolymer, polyoxyethylene alkyl ether phosphate, etc.

As the cationic surfactant to be supplementarily added to the leveling agent, alkyl quaternary ammonium salts or ethylene oxide adducts of these can be exemplified. Examples of nonionic surfactants to be supplementally added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene alkyl ether. Polyoxyalkylene-based surfactants such as phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyldimethylaminoacetic acid betaine , alkyl imidazoline and other amphoteric surfactants; and fluorine-based or silicone-based surfactants.

<hardener, hardening accelerator> Moreover, in order to assist hardening of a thermosetting resin, a hardening|curing agent, a hardening accelerator, etc. may be contained in the coloring composition of this invention as needed. As the curing agent, phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds, etc. are effective, but are not particularly limited to these as long as they are reactive with thermosetting resins As the hardener, any hardener can be used. Moreover, among these, the compound which has two or more phenolic hydroxyl groups in one molecule, and an amine type hardening|curing agent are mentioned preferably. As the hardening accelerator, for example, amine compounds (eg, dicyandiamine, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, -Methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (such as triethylbenzylammonium chloride, etc.), Blocked isocyanate compounds (such as dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds ( such as triphenylphosphine, etc.), guanamine compounds (such as melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (such as 2,4-diamino-6 -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ·Isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.) and the like. These may be used individually by 1 type, and may use 2 or more types together. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

<Other additive ingredients> In order to stabilize the viscosity over time, a storage stabilizer may be contained in the coloring composition of this invention. Moreover, in order to improve the adhesiveness with a transparent substrate, you may contain adhesion improvement agents, such as a silane coupling agent.

Examples of storage stabilizers include: quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and methyl ethers thereof; tert-butylcatechol; Organic phosphines such as ethyl phosphine and tetraphenyl phosphine; phosphites and the like. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant.

Examples of adhesion enhancers include vinyl silanes such as vinyl tris(β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane; γ-methacryloyloxy (meth)acrylic silanes such as propylpropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethyl Oxysilane, β-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-Epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxy Epoxysilanes such as propyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β( Aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane and other aminosilanes ; Silane coupling agents such as thiosilanes such as γ-mercaptopropyl trimethoxysilane and γ-mercaptopropyl triethoxysilane. 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.

<Manufacturing method of coloring composition> The coloring composition of the present invention can be preferably dispersed in various ways such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor. The means is to manufacture (colorant dispersion) by finely dispersing a colorant in a colorant carrier such as a resin and/or a solvent together with a dispersing aid such as a pigment derivative or a resin-type dispersant. In this case, two or more colorants and the like may be dispersed in the colorant carrier at the same time, or the resultant dispersed in the colorant carrier may be mixed. When the solubility of colorants such as dyes is high, specifically, if the solubility in the solvent used is high, it is dissolved by stirring, and foreign matter is not confirmed, it is not necessary to perform micronization as described above. dispersed to manufacture.

Moreover, when used as a photosensitive coloring composition (resist material), it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent-developing-type or alkali-developing-type coloring composition can be prepared by mixing the colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, an optional solvent, other dispersing aids, additives, and the like. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added to the prepared coloring composition afterward.

＜Dispersion Auxiliary＞ When dispersing the colorant in the colorant carrier, a dispersing aid such as a pigment derivative, a resin-type dispersant, and a surfactant may be appropriately contained. Since the dispersing aid has a great effect of preventing reagglomeration of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good lightness and viscosity stability. The pigment derivatives and resin-type dispersants are as described above.

＜Surfactant＞ Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, and alkylnaphthalenesulfonic acid. Sodium, Sodium Alkyl Diphenyl Ether Disulfonate, Monoethanolamine Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Ammonium Lauryl Sulfate, Monoethanolamine Stearate, Monoethanolamine of Styrene-Acrylic Acid Copolymer, Polyoxyethylene Alkane Anionic surfactants such as base ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan Nonionic surfactants such as alcohol monostearate and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; Amphoteric surfactants such as alkylbetaines such as betaine methylaminoacetate and alkylimidazolines can be used alone or in combination of two or more, but are not necessarily limited to these.

When adding a surfactant, it is preferable that it is 0.1-55 mass parts with respect to 100 mass parts of coloring agents, and it is more preferable that it is 0.1-45 mass parts. When the compounding quantity of surfactant is less than 0.1 mass part, the effect after addition is hard to be acquired, and when content exceeds 55 mass parts, dispersion|distribution may be affected by an excess dispersing agent.

<Removal of coarse particles> The coloring composition of the present invention preferably has coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm by means of centrifugal separation, filtration with a sintered filter or a membrane filter, or the like Removal of the above coarse particles and mixed dust. As described above, the coloring composition preferably does not substantially contain particles of 0.5 μm or more. More preferably, it is preferably 0.3 μm or less.

＜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 segment, a cyan filter segment, and a yellow filter segment. Regarding the color filter of the present invention, at least one of the red filter segments is formed from the pigment composition of the present invention.

<Manufacturing method of color filter> Color filters can be produced by printing or photolithography. As for the formation of the filter segment by the printing method, patterning can be achieved simply by repeating the printing and drying of the coloring composition prepared as the printing ink, so it is a low-cost and high-volume method for producing a color filter. Excellent productivity. Furthermore, the development of printing technology has enabled printing of fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to set it as a composition which does not dry and harden the ink on a printing plate or a blanket. In addition, it is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted by using a dispersant or an extender pigment.

In the case of forming the filter segment by photolithography, the solvent-developing or alkali-developing coloring is carried out by coating methods such as spray coating, spin coating, slit coating, and roll coating. The coloring composition prepared as a resist material is apply|coated on a transparent substrate so that a dry film thickness may become 0.2 micrometer - 5 micrometers. The film dried as needed is exposed (irradiated with radiation) through a mask with a predetermined pattern provided in a state of being in contact with or not in contact with the film. Then, it is immersed in a solvent or an alkaline developing solution, or the developing solution is sprayed by spraying, etc., to remove the uncured portion to form a desired pattern, and then repeat the same operation for other colors to manufacture a color filter. . Furthermore, in order to accelerate|stimulate the superposition|polymerization of a colored resist material, you may implement heating as needed. According to the photolithography method, a color filter with higher precision than the printing method can be manufactured.

At the time of image development, as an alkaline developing solution, aqueous solutions, such as sodium carbonate and sodium hydroxide, can also be used, and organic bases, such as dimethylbenzylamine and triethanolamine, can also be used. In addition, an antifoaming agent or a surfactant may 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-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be coated and dried to form an oxygen-resistant resin. The resulting polymer hindered film was then exposed to light.

In addition to the above-mentioned method, the color filter of the present invention may be produced by an electrowinning method, a transfer method, an inkjet method, or the like, and the coloring composition of the present invention may be used in any method. Furthermore, the electrodeposition method is a method of using a transparent conductive film formed on a substrate to electrodeposit various color filter segments on the transparent conductive film by electrophoresis of colloidal particles, thereby manufacturing a color filter. In addition, the transfer method is a method of forming a filter segment on the surface of a releasable transfer base sheet in advance, and transferring the filter segment to a desired substrate.

The black matrix can be formed in advance before forming the color filter segments 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, thin film transistors (Thin Film Transistor, TFT) can also be pre-formed on the transparent substrate or the reflective substrate, and then various color filter segments are formed. Moreover, on the color filter of this invention, an overcoat film, a transparent conductive film, etc. are formed as needed.

<Liquid crystal display device> The liquid crystal display device of the present invention includes the color filter of the present invention. The color filter of the present invention is bonded to the opposing substrate using a sealant, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or retardation film is attached to the outside of the substrate as necessary , thereby manufacturing a color liquid crystal display device. The color liquid crystal display device can be used in Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Compensated Bend (OCB) is used in a liquid crystal display mode that is colored by using a color filter.

<Solid-state imaging element> The solid-state imaging element of the present invention includes the color filter of the present invention. The structure of the solid-state imaging element of the present invention is a structure including the color filter for the solid-state imaging element of the present invention, and is not particularly limited as long as it functions as a solid-state imaging element, and examples thereof include the following structures. The structure is as follows: a plurality of photodiodes constituting a light-receiving area of a solid-state imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) The photodiode and the transmission electrode are provided with a light-shielding film including tungsten or the like opening only to the light-receiving portion of the photodiode, and the light-shielding film is provided with a light-shielding film covering the entire surface of the light-shielding film and the photodiode. A device protective film including silicon nitride or the like formed as a light-receiving portion has the color filter for a solid-state imaging element of the present invention on the device protective film. Furthermore, it can also be a structure in which a condensing unit (such as a microlens, etc.; the same below) is provided on the protective film of the device and below the color filter (closer to the substrate) or a color filter is provided with a condensing unit. unit structure, etc. Furthermore, the organic CMOS sensor is composed of a full-color photosensitive organic photoelectric conversion film including a thin film as a photoelectric conversion layer and a CMOS signal readout substrate, and is an organic material that captures light and converts it into an electrical signal. A hybrid structure of a two-layer structure that supports an inorganic material that functions to export an electrical signal to the outside can, in principle, make the aperture ratio 100% relative to incident light. The organic photoelectric conversion film is a continuous film with free structure and can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication process, and is suitable for the miniaturization of the filter section. The arrangement of the color filter segments is not particularly limited, and a known method can be used.

Moreover, the color filter of this invention can also be used for manufacture of a color imaging element, an organic electroluminescent display device, electronic paper, etc. other than a color liquid crystal display device. [Example]

Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto. In addition, in the Example, "part" and "%" represent "mass part" and "mass %", respectively. In addition, the average primary particle size of the pigment and the weight average molecular weight (Mw) of the resin are as follows.

(Average primary particle diameter of pigment) The average primary particle size of the pigment is determined by directly measuring the size of the primary particles from an electron microscope photograph using a transmission electron microscope (TEM). Specifically, the short-axis diameter and long-axis diameter of the primary particles of each pigment were measured, and the average was used as the particle diameter of the primary particles of the pigment. Next, about 100 or more pigment particles, the volume (mass) of each particle is obtained by approximating a cube of the obtained particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

(Resin weight average molecular weight (Mw)) The weight-average molecular weight (Mw) of the resin was determined by using a TSKgel column (manufactured by Tosoh) and using a Gel Permeation Chromatograph (GPC) equipped with an RI detector (Tosoh). Manufacturing, HLC-8120GPC), and the polystyrene conversion weight average molecular weight (Mw) measured using tetrahydrofuran (tetrahydrofuran, THF) as a developing solvent.

Next, the production methods of the resin solutions, resin-type dispersant solutions, dye derivatives, and colorants used in Examples and Comparative Examples will be described.

<Production of acrylic resin solution> (Preparation of Acrylic Resin Solution 1) 100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device in a separable four-necked flask, and heated to 120° C. while injecting nitrogen into the vessel. , at the stated temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentyl methacrylate, 16 parts of methyl methacrylate were added dropwise from the dropping tube over a period of 2.5 hours. A mixture of 1.0 parts of azobisisobutyronitrile as a catalyst required for the reaction of the precursor in the stage was subjected to a polymerization reaction. Next, the inside of the flask was replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of tris-dimethylaminomethylphenol and 0.3 parts of hydroquinone, which are catalysts required for the reaction of the precursors in this stage, were put into the flask. The reaction was carried out at 120° C. for 5 hours to obtain a resin solution having a weight average molecular weight of about 12,000 (measured by GPC). The acrylic acid and the epoxy group terminal of the glycidyl methacrylate structural unit to be charged are ester-bonded, so that no carboxyl group is generated in the resin structure. Furthermore, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine which is a catalyst required for the reaction of the precursor in this stage were added, and it was made to react at 120 degreeC for 4 hours. One of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride site of the added tetrahydrophthalic anhydride is ester-bonded with the hydroxyl group in the resin structure, and the other generates a carboxyl terminal. Acrylic resin solution 1 was obtained by adding propylene glycol monomethyl ether acetate so that the nonvolatile content might be 20%.

(Preparation of Acrylic Resin Solution 2) 100 parts by mass of propylene glycol monomethyl ether acetate was placed in a separable flask with a cooling tube, and after nitrogen substitution, the temperature was raised to 90°C. On the other hand, in the dropping tank 1, 10.0 parts of dimethyl-2,2'-[oxybis(methylenebis)]-2-propionate, 40.1 parts of cyclohexyl methacrylate, methyl methacrylate were mixed. 24.2 parts of tetrahydrofurfuryl base acrylate, 24.7 parts of methacrylic acid, 2.0 parts of 3-butyl peroxy-2-ethylhexanoate, and 80 parts of propylene glycol monomethyl ether acetate. In addition, 3.1 parts of (beta)-mercaptopropionic acid and 6 parts of propylene glycol monomethyl ether acetate were mixed in the dropping tank 2. While maintaining the reaction temperature at 90° C., the dropwise addition was performed at a constant rate from the dropping tank 1 and the dropping tank 2 to the reaction tank over 2.5 hours. After completion of the dropwise addition, the temperature was maintained at 90°C for 30 minutes, then 0.5 part of tert-butyl peroxy-2-ethylhexanoate was added, and the reaction was continued at 90°C for 30 minutes. Then, the reaction temperature was raised to 115°C, and the reaction was continued for 1.5 hours. After temporarily cooling to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 parts of 6-tert-butyl-2,4-xylenol, and 0.38 parts of dimethylbenzylamine were charged, and the oxygen concentration was adjusted to 7%. The nitrogen-air mixed gas was bubbled, and the temperature was raised to 110° C., and the reaction was carried out for 6 hours. Then, the temperature was raised to 115°C and reacted for 2 hours to complete the reaction, cooled to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes, and the non-volatile components were measured. Acrylic resin solution 2 was obtained by adding propylene glycol monomethyl ether acetate so that the volatile content would be 20% by mass. The weight average molecular weight of the resin was 9000, and the acid value per solid content was 70 mgKOH/g.

<Production of resin type dispersant solution> (Preparation of Resin Type Dispersant Solution 1) 1.0 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) and 186 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask including a cooling pipe and a stirrer, and then, 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate portion, and nitrogen replacement was performed for 30 minutes. Then, the temperature of the reaction solution was raised to 60° C. with gentle stirring, and the temperature was maintained for 24 hours to perform living radical polymerization. Next, a solution obtained by dissolving 1.0 parts by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate in 70 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen for 30 minutes was added to the reaction solution. , living radical polymerization was carried out at 60° C. for 24 hours, thereby obtaining a solution of the block copolymer. To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added, reacted at 80° C. for 2 hours, and the solid content concentration was adjusted to 40%, thereby obtaining a resinous dispersion. agent solution 1. Resin-type dispersant 1 is a block copolymer comprising an A block and a B block, the A block having a compound derived from methacryloyloxyethylbenzyldimethylammonium chloride and dimethylmethacrylate A repeating unit of aminoethyl ester, the B block has repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate. Regarding the results of proton nuclear magnetic resonance (NMR) measurement, the copolymerization ratio of each repeating unit is methacryloyloxyethylbenzyldimethylammonium chloride/dimethylaminoethyl methacrylate/ Methyl methacrylate/butyl methacrylate/2-ethylhexyl methacrylate/benzyl methacrylate=34/4/18/18/14/12 (mass ratio).

(Preparation of Resin Type Dispersant Solution 2) Into a reaction vessel including a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, methoxyacetic acid were charged 41.8 parts of propyl esters were replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by the measurement of the acid value, the temperature in the system was cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and tertiary butyl acrylate were charged. 16.0 parts of esters, 10.0 parts of (3-ethyloxetan-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate, and 0.10 parts of 2,2'-azobisisobutyronitrile and acetic acid were added 60.0 parts of methoxypropyl esters were reacted for 10 hours. It was confirmed by solid content measurement that 95% of the polymerization had proceeded, and the reaction was terminated to obtain a polyester dispersant having an acid value of 47 mgKOH/g and a number average molecular weight of 15,000. To this, methoxypropyl acetate was added so that a solid content might become 40% by solid content measurement, and the resin type dispersant solution 2 which has an aromatic carboxyl group was obtained.

(Preparation of Resin Type Dispersant Solution 3) As the resin-type dispersant solution 3, the commercially available "Disperbyk-110 (solid content 52%)" manufactured by BYK-Chemie was used.

<Manufacture of dye derivatives>

色素衍生物1(Production of Dye Derivative 1) With reference to Synthesis Example 3 of Japanese Patent No. 5748665, a dye derivative 1 represented by the following structure was produced. [hua 8]

Pigment Derivative 1

色素衍生物2(Production of Dye Derivative 2) As the dye derivative 2, the organic dye derivative (D4) of Japanese Patent Laid-Open No. 2010-163500 was used. [Chemical 9]

Pigment Derivative 2

(Production of Dye Derivative 3) The dye derivative 3 was obtained according to the synthesis method described in Japanese Patent Laid-Open No. 2004-067715. [Chemical 10]

色素衍生物4(Production of Dye Derivative 4) With reference to Production Example 6 of Japanese Patent No. 4983061, a dye derivative 4 represented by the following structure was produced. [Chemical 11]

Pigment Derivative 4

<Manufacturing method of colorant> <Production of diketopyrrolopyrrole pigment of general formula (2)> (Production of Diketopyrrolopyrrole Pigment (A2-1)) In a nitrogen atmosphere, 200 parts of tertiary amyl alcohol and 140 parts of tertiary amyl alcohol sodium dehydrated by molecular sieve 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, 88 parts of diisopropyl succinate and 122.5 parts of 4-propyl benzonitrile were put into a glass flask, and heated to 90 degreeC, stirring, and it melt|dissolved, and the solution of these mixtures was prepared. The heated solution of the mixture was gradually added dropwise to the alkoxide solution heated to 100° C. at a constant speed 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 a diketopyrrolopyrrole-based compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were put into a reaction container with a glass jacket, and cooled to -10°C. To this cooled mixture, while rotating a shear disk with a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser, a small amount of the previously obtained diketopyrrolopyrrole-based compound cooled to 75° C. was added thereto. Alkali metal salt solution. At this time, while cooling so that the temperature of the mixture containing methanol, acetic acid and water is always kept at -5°C or lower, the addition rate of the alkali metal salt of the diketopyrrolopyrrole-based compound at 75°C was adjusted while adjusting the rate of addition. A small amount was added gradually over a period of about 120 minutes. After the alkali metal salt was added, red crystals were precipitated to form a red suspension. Next, the obtained red suspension was washed with an ultrafiltration apparatus at 5° C., and then filtered and separated to obtain a red paste. The paste was redispersed in 3,500 parts of methanol cooled to 0°C to prepare a suspension having a methanol concentration of about 90%, and stirred at 5°C for 3 hours to perform particle sizing and washing accompanied by crystal transfer. Next, the water paste of the obtained diketopyrrolopyrrole-based compound was dried at 80° C. for 24 hours by filtration separation using an ultrafiltration machine, and pulverized to obtain a compound of the following formula (A2-1). 129.6 parts of diketopyrrolopyrrole pigments.

式（A2-1）[Chemical 12]

Formula (A2-1)

(Production of Diketopyrrolopyrrole Pigment (A2-2)) The following formula ( 135.4 parts of diketopyrrolopyrrole pigments represented by A2-2).

式（A2-2）[Chemical 13]

Formula (A2-2)

(Production of Diketopyrrolopyrrole Pigment (A2-3)) The following formula ( 133.4 parts of diketopyrrolopyrrole pigments represented by A2-3).

式（A2-3）[Chemical 14]

Formula (A2-3)

(Production of Diketopyrrolopyrrole Pigment (A2-4)) Except having changed 122.5 parts of 4-propylbenzonitrile to 181.7 parts of 4-(2-ethylhexyl)benzonitrile, it carried out similarly to manufacture of diketopyrrolopyrrole pigment (A2-1), and obtained the following 173.3 parts of diketopyrrolopyrrole pigments represented by the formula (A2-4).

式（A2-4）[Chemical 15]

Formula (A2-4)

(Production of Diketopyrrolopyrrole Pigment (A2-5)) The following formula ( 206.2 parts of diketopyrrolopyrrole pigments represented by A2-5).

式（A2-5）[Chemical 16]

Formula (A2-5)

(Production of Diketopyrrolopyrrole Pigment (A2-6)) The following formula ( A2-6) 238.8 parts of diketopyrrolopyrrole pigments.

式（A2-6）[Chemical 17]

Formula (A2-6)

<Manufacture of other diketopyrrolopyrrole pigments> (Production of Diketopyrrolopyrrole Pigment (A3-1)) In the reaction container 1, 220 parts of tertiary amyl alcohols were added, 32 parts of 60% NaH were added while cooling in a water bath, and the mixture was heated and stirred at 90°C. Next, 100 parts of tertiary amyl alcohols were heated and dissolved in the reaction vessel 2, and 99.2 parts of compounds of the following formula (700) synthesized by the method of "Tetrahedron", 58 (2002) 5547-5565 and the formula (N-1) 71.8 parts of benzonitrile compounds were dripped into the reaction container 1 over 2 hours. The reaction was carried out at 120° C. for 10 hours, then cooled to 60° C., and 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration separation and methanol washing to obtain 79.1 parts of the diketopyrrolopyrrole pigment represented by the formula (A3-1). .

式（700）

式（N-1）[Chemical 18]

formula (700)

Formula (N-1)

式（A3-1）[Chemical 19]

Formula (A3-1)

<Production of diketopyrrolopyrrole pigment composition> [Example 1] (Production of Diketopyrrolopyrrole Pigment Composition (P-1)) 97.0 parts of CI Pigment Red 254 ("Cinilex DPP Red ST" from CINIC), 3.0 parts of formula (A2-1), 1000 parts of sodium chloride and 120 parts of diethylene glycol It was put into a 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho), and kneaded at 60° C. for 12 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80° C. to form a slurry, filtered and washed with water to remove salt and diethylene glycol, and then heated at 80° C. By drying all day and night, and pulverizing, 98.3 parts of diketopyrrolopyrrole pigment compositions (P-1) were obtained. The average primary particle diameter was 28.5 nm.

[Example 2 to Example 14] (Production of diketopyrrolopyrrole pigment compositions (P-2 to P-14)) Except that "CI Pigment Red 254 ("Cinilex DPP Red ST" from CINIC) 97.0 parts, formula (A2-1) 3.0 parts" was changed to the diketopyrrolo described in Table 1 The diketopyrrolopyrrole pigment compositions (P-2 to P-14) were obtained by the same method as in Example 1 except for the types and amounts of the pyrrole pigment and the pigment derivative. The average primary particle size of each pigment composition is as described in Table 1.

[Comparative Example 1 to Comparative Example 6] (Manufacture of diketopyrrolopyrrole pigment compositions (P-S1 to P-S6)) Except that "CI Pigment Red 254 ("Cinilex DPP Red ST" from CINIC) 97.0 parts, formula (A2-1) 3.0 parts" was changed to the diketopyrrolo described in Table 1 The diketopyrrolopyrrole pigment compositions (P-S1 to P-S6) were obtained by the same method as in Example 1 except for the types and amounts of the pyrrole pigment and the pigment derivative. The average primary particle size of each pigment composition is as described in Table 1.

[Table 1] Pigment composition Composition of Diketopyrrolopyrrole Pigment Composition Average primary particle diameter (nm) Diketopyrrolopyrrole Pigments Pigment Derivatives General formula (1) parts by mass General formula (2) parts by mass other parts by mass type parts by mass Example 1 P-1 PR254 97.0 Formula (A2-1) 3.0 - - - - 28.5 Example 2 P-2 PR254 97.0 Formula (A2-2) 3.0 - - - - 27.8 Example 3 P-3 PR254 97.0 Formula (A2-3) 3.0 - - - - 27.2 Example 4 P-4 PR254 97.0 Formula (A2-4) 3.0 - - - - 29.4 Example 5 P-5 PR254 97.0 Formula (A2-5) 3.0 - - - - 30.9 Example 6 P-6 PR254 97.0 Formula (A2-6) 3.0 - - - - 31.2 Example 7 P-7 PR254 99.9 Formula (A2-2) 0.1 - - - - 28.0 Example 8 P-8 PR254 99.5 Formula (A2-2) 0.5 - - - - 28.1 Example 9 P-9 PR254 99.0 Formula (A2-2) 1.0 - - - - 27.6 Example 10 P-10 PR254 95.0 Formula (A2-2) 5.0 - - - - 27.5 Example 11 P-11 PR254 90.0 Formula (A2-2) 10.0 - - - - 28.9 Example 12 P-12 PR254 99.0 Formula (A2-2) 1.0 - - Pigment Derivative 2 5.0 26.5 Example 13 P-13 PR291 99.0 Formula (A2-2) 1.0 - - - - 29.2 Example 14 P-14 PR291 99.0 Formula (A2-2) 1.0 - - Pigment Derivative 1 5.0 26.1 Comparative Example 1 P-S1 PR254 100.0 - - - - - - 33.4 Comparative Example 2 P-S2 PR254 85.0 Formula (A2-2) 15.0 - - - - 31.3 Comparative Example 3 P-S3 PR254 97.0 - - PR272 3.0 - - 29.5 Comparative Example 4 P-S4 PR254 97.0 - - Formula (A3-1) 3.0 - - 30.3 Comparative Example 5 P-S5 PR291 100.0 - - - - - - 33.1 Comparative Example 6 P-S6 PR291 85.0 Formula (A2-2) 15.0 - - - - 29.8 PR254: "Cinilex DPP Red ST" from CINIC PR291: "Cinilex DPP Red MT-CF" from CINIC PR272: BASF "Irgazin RED K3800"

<Manufacture of diketopyrrolopyrrole coloring composition> [Example 101] (Production of diketopyrrolopyrrole coloring composition (DR-1)) The mixture of the following composition was stirred and mixed so as to become homogeneous, and then a "mini model" manufactured by Eiger-mill (Eiger Japan) was used using zirconia beads having a diameter of 0.5 mm. ) M-250 MKII") was dispersed for 5 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (DR-1). Diketopyrrolopyrrole pigment composition (P-1) 10.7 parts Pigment Derivatives 1 Pigment Derivatives 4           0.3 copies Resin type dispersant solution 1         6.0 parts Resin type dispersant solution 2         6.0 parts Resin type dispersant solution 3           1.0 part Acrylic resin solution 1           13.4 parts Propylene glycol monomethyl ether acetate 56.6 parts Propylene Glycol Monomethyl Ether 5.0 parts

[Example 102 to Example 114, Comparative Example 101 to Comparative Example 106] (Production of diketopyrrolopyrrole coloring compositions (DR-2 to DR-14, DR-S1 to DR-S6)) Colored compositions (DR-2 to DR- 14. DR-S1~DR-S6).

<Manufacture of other coloring compositions> (Manufacture of PR177 Coloring Composition for Toning (DR-177A)) The following mixture was stirred and mixed so as to become homogeneous, and zirconia beads having a diameter of 0.5 mm were used to make the mixture using an Eiger-mill (“mini model M” manufactured by Eiger Japan Co., Ltd.). -250 MKII") was dispersed for 5 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a PR177 coloring composition (DR-177A). Anthraquinone Pigment ("Cinilex Red SR3C" from CINIC) 11.6 copies Pigment Derivatives 3             0.4 Resin type dispersant solution 1         6.0 parts Resin type dispersant solution 2           6.0 parts Acrylic resin solution 2           16.0 parts Propylene Glycol Monomethyl Ether Acetate 55.0 parts Propylene Glycol Monomethyl Ether 5.0 parts

<Evaluation of coloring composition> The obtained coloring compositions (DR-1 to DR-14, DR-S1 to DR-S6) were evaluated by the following method. The results are shown in Table 2.

(evaluation of contrast ratio) Using a spin coater, apply the coloring compositions (DR-1 to DR-14, DR-S1 to DR-S6) on a glass substrate with a thickness of 100 mm × 100 mm and a thickness of 1.1 mm. The solvent was removed by heating at °C for 15 minutes, heated at 230 °C for 60 minutes in a clean oven, and left to cool to obtain a red coated substrate. Furthermore, after the heat treatment of the red coating film substrate at 230° C., the chromaticity of x=0.660 under the C light source was satisfied. Next, the measuring method of a contrast ratio is demonstrated. The light emitted from the backlight unit for liquid crystal displays is polarized by the polarizing plate, and reaches the polarizing plate through the dried coating film of the coloring composition applied on the glass substrate. When the polarizing plate is parallel to the polarizing plane of the polarizing plate, light is transmitted through the polarizing plate, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dry coating film of the coloring composition, scattering due to the pigment particles, etc., and if a part of the polarizing plane is shifted, when the polarizing plate is parallel, the amount of light passing through the polarizing plate decreases. When the polarizers are orthogonal, part of the light passes through the polarizers. The transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were orthogonal was calculated. In addition, as a luminance meter, a color luminance meter ("BM-5A" manufactured by Topcon) was used, and as a polarizing plate, a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used. In addition, in order to block excess light during measurement, a black mask with a 1 cm square hole was interposed in the measurement part. (contrast ratio) = (brightness when parallel) / (brightness when orthogonal) The contrast ratio was evaluated in the following four stages. ◎: 5000 or more (extremely good) ○: 4000 or more, less than 5000 (good: usable) △: 3000 or more, less than 4000 (defective) ×: Less than 3000 (extremely bad)

(Evaluation of storage stability) About the coloring compositions (DR-1 to DR-14, DR-S1 to DR-S6), the initial viscosity at 25° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Then, it was stored in a thermostat at 40°C for two weeks and accelerated with time, then the viscosity after time was measured by the same method as the viscosity measurement, and the rate of change of the viscosity before and after storage at 40°C for two weeks was calculated, The evaluation was performed in three stages according to the following criteria. ◎: When the absolute value of the viscosity change rate is less than 10% (good) ○: When the absolute value of the viscosity change rate is 10% to 20% (normal) ×: When the absolute value of the viscosity change rate exceeds 20% (defective)

[Table 2] coloring composition Pigment composition Evaluation results of coloring compositions contrast ratio storage stability Example 101 DR-1 P-1 ○ ◎ Example 102 DR-2 P-2 ◎ ◎ Example 103 DR-3 P-3 ◎ ◎ Example 104 DR-4 P-4 ◎ ◎ Example 105 DR-5 P-5 ◎ ◎ Example 106 DR-6 P-6 ◎ ○ Example 107 DR-7 P-7 ○ ◎ Example 108 DR-8 P-8 ○ ◎ Example 109 DR-9 P-9 ○ ◎ Example 110 DR-10 P-10 ◎ ◎ Example 111 DR-11 P-11 ○ ○ Example 112 DR-12 P-12 ◎ ◎ Example 113 DR-13 P-13 ○ ◎ Example 114 DR-14 P-14 ◎ ◎ Comparative Example 101 DR-S1 P-S1 × ◎ Comparative Example 102 DR-S2 P-S2 ○ × Comparative Example 103 DR-S3 P-S3 × ◎ Comparative Example 104 DR-S4 P-S4 △ ○ Comparative Example 105 DR-S5 P-S5 × ◎ Comparative Example 106 DR-S6 P-S6 ○ ×

As shown in Table 2, the coloring composition using the diketopyrrolopyrrole pigment composition of the present invention was a result of favorable contrast ratio and storage stability.

<The manufacturing method of the photosensitive coloring composition> [Example 201] (Manufacture of photosensitive coloring composition (RR-1)) The mixture of the following composition was uniformly stirred and mixed, and then filtered through a filter with a pore diameter of 1.0 μm to obtain a red photosensitive coloring composition (RR-1). PR177 coloring composition (DR-177A) 16.28 parts Diketopyrrolopyrrole coloring composition (DR-1) 33.72 parts 3.60 parts of acrylic resin solution Epoxy compound ("EHPE-3150" made by Daicel) 0.16 parts Photopolymerizable monomer ("Aronix (M402)" manufactured by Toagosei Corporation) 1.10 parts Photopolymerizable monomer ("Aronix M350" manufactured by Toa Gosei Corporation) 1.45 parts Photopolymerization initiator ("IRGACURE OXE02" manufactured by BASF)         0.15 parts Photopolymerization initiator ("IRGACURE 369" manufactured by BASF) 0.30 parts Sensitizer ("KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.) 0.05 copies Thiol compound (pentaerythritol tetrathiopropionate) 0.20 part Leveling agent ("BYK-330" manufactured by BYK-Chemie) 0.05 copies Antioxidant ("IRGANOX 1010" manufactured by BASF) 0.10 parts Propylene Glycol Monomethyl Ether Acetate 32.84 parts Ethyl 3-ethoxypropionate 10.00 parts

[Example 202 to Example 214, Comparative Example 201 to Comparative Example 206] (Manufacture of photosensitive coloring compositions (RR-2 to RR-14, RR-S1 to RR-S6)) A photosensitive coloring composition (RR-2) was obtained in the same manner as in Example 201, except that the total content of the coloring compositions in the photosensitive coloring composition was all fixed at 50.00 parts, and the types and mixing ratios of the coloring compositions were changed. ~RR-14, RR-S1~RR-S6). The type of the coloring composition was as shown in Table 3, and the mixing ratio of the coloring composition was a ratio in which the chromaticity after substrate preparation was (x=0.660, y=0.324) under a C light source.

[Example 215] (Manufacture of photosensitive coloring composition (RR-15)) The mixture having the following composition was uniformly stirred and mixed, and then filtered through a filter with a pore size of 1.0 μm to obtain a red photosensitive coloring composition (RR-15). PR177 coloring composition (DR-177A) 15.09 parts Diketopyrrolopyrrole coloring composition (DR-14) 34.91 parts 3.85 parts of acrylic resin solution 1 Epoxy compound (“TEPIC-S” manufactured by Nissan Chemical Industry) 0.16 parts Photopolymerizable monomer ("KAYARAD DPCA-30" manufactured by Nippon Kayaku Co., Ltd.)             1.85 parts Photopolymerizable monomer ("UA-510H" manufactured by Kyoeisha Chemical Co., Ltd.) 0.50 parts Photopolymerization initiator ("IRGACURE OXE01" manufactured by BASF)           0.55 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF) 0.20 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.05 part Silane coupling agent ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.) 0.03 parts Polymerization inhibitor (methyl hydroquinone) 0.02 part Ultraviolet absorber ("TINUVIN P" manufactured by BASF) 0.05 copies Leveling agent ("Megafac F-551" manufactured by DIC Co., Ltd.) 0.05 copies Propylene Glycol Monomethyl Ether Acetate 32.69 parts 1,3-Butanediol diacetate 5.00 parts 3-Methoxybutanol 5.00 parts

<Evaluation of a photosensitive coloring composition> About the obtained photosensitive coloring composition, it evaluated by the following method. The results are shown in Table 3. (Evaluation of Brightness) Using a spin coater, the photosensitive coloring compositions (RR-1 to RR-15, RR-S1 to RR-S6) were applied on a glass substrate of 100 mm×100 mm and 1.1 mm thick , heated at 80° C. for 15 minutes in a clean oven to remove the solvent to obtain a coating film. Next, ultraviolet exposure was performed using an ultra-high pressure mercury lamp with a cumulative light amount of 100 mJ/cm ² , and development was performed with an alkaline developer at 23° C. to obtain a coated substrate. Next, after heating at 230° C. for 30 minutes in a clean oven, and standing to cool, the resulting coating film substrate was measured for Brightness Y (C). Furthermore, after the heat treatment of the red coating film substrate at 230° C., the chromaticity was (x=0.660, y=0.324) under the C light source. As an alkaline developer, one containing 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of an anionic surfactant (“Pelex NBL” manufactured by Kao Corporation), and 90% by mass of water was used. developer. The evaluation of lightness was performed in the following four stages. ◎: 18.5 or more (extremely good) ○: 18.3 or more, less than 18.5 (good) △: 18.1 or more, less than 18.3 (bad) ×: less than 18.1 (extremely bad)

(evaluation of contrast ratio) The contrast ratio measurement was implemented using the board|substrate used for lightness evaluation. The evaluation of the contrast ratio was performed in the following four stages. ◎: 5000 or more (extremely good) ○: 4000 or more, less than 5000 (good) △: 3000 or more, less than 4000 (defective) ×: Less than 3000 (extremely bad)

(Evaluation of storage stability) About the obtained photosensitive coloring composition, the initial viscosity in 25 degreeC was measured using the E-type viscometer ("ELD type viscometer" by Toki Sangyo Co., Ltd.). Then, it was stored in a thermostat at 40°C for two weeks and accelerated with time, then the viscosity after time was measured by the same method as the viscosity measurement, and the rate of change of the viscosity before and after storage at 40°C for two weeks was calculated, The evaluation was performed in three stages according to the following criteria. ◎: When the absolute value of the viscosity change rate is less than 5% (good) ○: When the absolute value of the viscosity change rate is 5% to 10% (normal) ×: When the absolute value of the viscosity change rate exceeds 10% (defective)

(Evaluation of Heat Resistance) Using a spin coater, the photosensitive coloring compositions (RR-1 to RR-15, RR-S1 to RR-S6) were applied to a glass substrate of 100 mm×100 mm and 1.1 mm thick Then, the solvent was removed by heating at 70° C. for 15 minutes in a clean oven to obtain a dry coating film. At this time, coating was performed so that the dry coating film would be 2.5 μm. Then, using an ultra-high pressure mercury lamp, a mask with a stripe pattern of 100 μm width (pitch 200 μm) was exposed to ultraviolet rays with a cumulative light amount of 100 mJ/cm ² , and developed with an alkaline developer at 23 ° C to obtain striped patterns. Coated substrates. Next, heat treatment was performed at 230° C. for 60 minutes, then further heat treatment was performed at 240° C. for 60 minutes, and heat treatment was performed at 280° C. for 60 minutes. The coating film surface of the heat-treated substrate was observed with an optical microscope, and the presence or absence of crystal precipitation was determined according to the following four-step criteria. ◎…No crystal precipitation after heat treatment at 230°C for 60 minutes, after heat treatment at 240°C for 60 minutes and at 280°C for 60 minutes ○…After heat treatment at 230°C for 60 minutes and at 240°C There is no crystal precipitation after heat treatment at 280°C for 60 minutes, but there is crystal precipitation after heat treatment at 280°C for 60 minutes , with crystal precipitation ×... after heat treatment at 230 ° C for 60 minutes, crystal precipitation

(Evaluation of Solvent Resistance) Using a spin coater, the photosensitive coloring compositions (RR-1 to RR-15, RR-S1 to RR-S6) were coated on glass of 100 mm×100 mm and 1.1 mm thick On the substrate, the solvent was removed by heating at 70° C. for 15 minutes in a clean oven to obtain a dry coating film. At this time, coating was performed so that the dry coating film would be 2.5 μm. Then, using an ultra-high pressure mercury lamp, a mask with a stripe pattern of 100 μm width (pitch 200 μm) was exposed to ultraviolet rays with a cumulative light amount of 100 mJ/cm ² , and developed with an alkaline developer at 23 ° C to obtain striped patterns. Coated substrates. Next, heat treatment was performed at 230° C. for 60 minutes in a clean oven. Here, the chromaticity (L*(1), a*(1), b*(1)) under the C light source was measured, and then, at 40°C, N-methylpyrrolidone (N-methylpyrrolidone) pyrrolidone, NMP) for 30 minutes, and then the chromaticity (L*(2), a*(2), b*(2)) under the C light source was measured. Using the chromaticity values before and after the NMP immersion, the color difference ΔE*ab was calculated according to the following calculation formula, and the solvent resistance of the coating film was evaluated in the following three steps. Calculation formula: ΔE*ab=[[L*(2)-L*(1)] ² +[a*(2)-a*(1)] ² +[b*(2)-b*(1) ] ² ] ^1/2 ◎: ΔE*ab is less than 1.0 (extremely good) ○: ΔE*ab is 1.0 or more and less than 3.0 (good) △: ΔE*ab is 3.0 or more and less than 5.0 (bad) ×: ΔE*ab is 5.0 or more (extremely poor)

(Evaluation of dye migration property) The photosensitive coloring composition was apply|coated on a glass substrate using a slit die coater, and prebaking was performed for 2 minutes with a 90 degreeC hotplate, and the coating film with a film thickness of 2.4 micrometers was formed. Then, the substrate on which the coating film was formed was cooled to room temperature, and then, using a high-pressure mercury lamp, the coating film was exposed to each of 365 nm, 405 nm, and 436 nm at an exposure amount of 1,000 J/m ² through a striped mask. wavelength of radiation. After performing alkali development, washing with ultrapure water, and post-baking at 230° C. for 20 minutes, red striped pixels were formed on the substrate. Next, the transmittance (T1) at 520 nm on the glass substrate at a distance of 8 μm from the red stripe-shaped pixel was measured. Furthermore, the acrylic resin solution 2 was applied on the substrate using a slot die coater, and then prebaked for 2 minutes on a hot plate at 90° C. to form a coating film having a thickness of 2.5 μm. Furthermore, post-baking was performed at 230 degreeC for 20 minutes. Next, the transmittance (T2) at 520 nm on the glass substrate at a distance of 8 μm from the red stripe-shaped pixel was measured. The numerical difference between T1 and T2 was defined as ΔT (%), and the evaluation was performed in the following four stages. The smaller the ΔT value, the less the decrease in luminance due to the color migration to the adjacent filter segments of other colors, and it can be said that the dye migration is suppressed. ◎: ΔT is less than 1.0% (extremely good) ○: ΔT is 1.0% or more, less than 2.0% (good) △: ΔT is 2.0% or more, less than 3.0% (bad) ×: ΔT is 3.0% or more (extremely good) bad)

[table 3] Photosensitive coloring composition Diketopyrrolopyrrole Coloring Composition PR177 Coloring Composition Evaluation results of photosensitive coloring compositions name Pigment composition name lightness contrast ratio storage stability heat resistance Solvent resistance Migration Example 201 RR-1 DR-1 P-1 DR-177A 〇 〇 ◎ 〇 ◎ ◎ Example 202 RR-2 DR-2 P-2 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Example 203 RR-3 DR-3 P-3 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Example 204 RR-4 DR-4 P-4 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Example 205 RR-5 DR-5 P-5 DR-177A 〇 ◎ ◎ ◎ 〇 〇 Example 206 RR-6 DR-6 P-6 DR-177A 〇 ◎ 〇 ◎ 〇 〇 Example 207 RR-7 DR-7 P-7 DR-177A ◎ 〇 ◎ 〇 ◎ ◎ Example 208 RR-8 DR-8 P-8 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Example 209 RR-9 DR-9 P-9 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Example 210 RR-10 DR-10 P-10 DR-177A 〇 ◎ ◎ ◎ 〇 ◎ Example 211 RR-11 DR-11 P-11 DR-177A 〇 〇 〇 ◎ 〇 〇 Example 212 RR-12 DR-12 P-12 DR-177A 〇 ◎ ◎ ◎ ◎ ◎ Example 213 RR-13 DR-13 P-13 DR-177A ◎ 〇 ◎ ◎ ◎ ◎ Example 214 RR-14 DR-14 P-14 DR-177A ◎ ◎ ◎ ◎ ◎ ◎ Example 215 RR-15 DR-14 P-14 DR-177A ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 201 RR-S1 DR-S1 P-S1 DR-177A △ × ◎ × ◎ ◎ Comparative Example 202 RR-S2 DR-S2 P-S2 DR-177A × 〇 × ◎ × △ Comparative Example 203 RR-S3 DR-S3 P-S3 DR-177A △ × ◎ × ◎ ◎ Comparative Example 204 RR-S4 DR-S4 P-S4 DR-177A △ △ 〇 △ ○ 〇 Comparative Example 205 RR-S5 DR-S5 P-S5 DR-177A △ × ◎ × ◎ ◎ Comparative Example 206 RR-S6 DR-S6 P-S6 DR-177A × 〇 × ◎ × △

As shown in Table 3, as a feature of the present invention, Example 201 containing the diketopyrrolopyrrole pigments of the general formula (1) and the general formula (2) in a mass ratio of 99.9:0.1 to 90.0:10.0 The lightness, contrast ratio, storage stability, heat resistance, solvent resistance, and dye migration properties of the photosensitive coloring composition of Example 215 had no practical problems and were particularly good results. On the other hand, in Comparative Example 210, Comparative Examples 203 to 205, which do not contain the diketopyrrolopyrrole pigment of the general formula (2), the crystallization in the heating step was poor compared with the Examples, due to the influence of the crystallization. As a result, the brightness and contrast ratio are also inferior to those of the examples. In addition, Comparative Example 202 or Comparative Example 206 containing the diketopyrrolopyrrole pigment of the general formula (2) in an amount of more than 10% by mass was inferior in stability, solvent resistance, and dye migration to the Examples. The reason for this is considered to be that the diketopyrrolopyrrole pigment of the general formula (2) itself has poor dispersion stability, solvent resistance, and dye migration properties compared with the diketopyrrolopyrrole pigment of the general formula (1).

＜Production of color filter＞ First, green and blue photosensitive coloring compositions for producing a color filter are produced.

(Production of green photosensitive coloring composition (RG-100)) The mixture of the following composition was stirred and mixed so as to become homogeneous, and then a "mini model" manufactured by Eiger-mill (Eiger Japan) was used using zirconia beads having a diameter of 0.5 mm. ) M-250 MKII”) was dispersed for 5 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a green coloring composition (DG-100). Green Pigment (C.I. Pigment Green 58) 8.6 parts Yellow Pigment (C.I. Pigment Yellow 138) 3.4 parts Resin type dispersant ("EFKA (EFKA) 4300" manufactured by BASF) 3.0 copies 25.0 parts of acrylic resin solution Propylene Glycol Monomethyl Ether Acetate 52.0 parts

Next, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the filter of 1.0 micrometers of pore diameters, and produced the green photosensitive coloring composition (RG-100). Green coloring composition (DG-100) 42.0 parts Acrylic resin solution 1           13.2 parts Photopolymerizable monomer ("Aronix (M402)" manufactured by Toagosei Corporation) 2.8 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 part Propylene Glycol Monomethyl Ether Acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-100)) The mixture of the following composition was stirred and mixed so as to become homogeneous, and zirconia beads having a diameter of 0.5 mm were used in an eiger mill (“mini model” manufactured by Eiger Japan Co., Ltd.). M-250 MKII") was dispersed for 5 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a blue colored composition (DB-100). Blue Pigment (C.I. Pigment Blue 15:6) 7.2 parts Purple Pigment (C.I. Pigment Violet 23) 4.8 parts Resin type dispersant ("EFKA (EFKA) 4300" manufactured by BASF) 1.0 parts 35.0 parts of acrylic resin solution 1 Propylene Glycol Monomethyl Ether Acetate 52.0 parts

Next, the mixture of the following composition was stirred and mixed so that it might become uniform, and it filtered with the filter of 1.0 micrometers of pore diameters, and produced the blue photosensitive coloring composition (RB-100). Blue coloring composition (DB-100) 34.0 parts Acrylic resin solution 2         15.2 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toa Gosei Corporation) 3.3 parts Photopolymerization initiator ("IRGACURE 907" manufactured by BASF) 2.0 copies Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 part Propylene Glycol Monomethyl Ether Acetate 45.1 parts

(Production of Color Filter for Liquid Crystal Display Device) A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-14) of the present invention is applied on the substrate by a spin coater to form Tinted film. The film was irradiated with ultraviolet rays of 200 mJ/cm ² using an ultra-high pressure mercury lamp through a light shield. Next, the unexposed portion was removed by spray development with an alkaline developer containing a 0.2 mass % sodium carbonate aqueous solution, and then washed with ion-exchanged water, and the substrate was heated at 230° C. for 30 minutes to form a red filter. section. Here, the red filter segment is set to satisfy the chromaticity of x=0.660 under the C light source after the heat treatment at 230°C. In addition, by the same method, a green filter segment was formed using a green photosensitive coloring composition (RG-100) so as to satisfy the chromaticity of y=0.570, and a blue photosensitive coloring composition (RB-100) was used. The blue filter segments are formed so as to satisfy the chromaticity of y=0.045, and each filter segment is formed to obtain a color filter.

By using the photosensitive coloring composition (RR-14) of the present invention for the formation of the red filter segment, it is possible to achieve high brightness and high contrast of the color filter, and there are no problems in other physical properties. and can be used appropriately. In addition, the color filter of the present invention is bonded to the opposing substrate using a sealant, the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and the polarizing film or retardation film is bonded to the outside of the substrate. In this way, a liquid crystal display device excellent in the ratio of brightness to contrast was obtained.

(Production of color filters for solid-state imaging elements) On a 6-inch silicon wafer, a resist solution for flattening film (HL-18s; manufactured by Nippon Steel Chemical Co., Ltd.) was applied by spin coating, and was pre-baked using a 100°C hot plate. 6 minutes heat treatment. Furthermore, it processed in the oven at 230 degreeC for 1 hour, the coating film was hardened, the planarization film of 1.0 micrometers was formed, and the wafer with the planarization film was obtained.

The green photosensitive coloring composition (RG-100) was apply|coated on the silicon wafer with a planarization film by a spin coater, and it heat-processed for 1 minute with a 100 degreeC hotplate as prebaking. The film thickness after prebaking was adjusted to 0.9 μm.

Next, at a wavelength of 365 nm using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.), through a mask for forming red pixels of 1.0 μm square, the exposure amount was 150. mJ/cm ² for pattern exposure.

The exposed coating film was subjected to liquid coating development for 1 minute with an organic alkali developer. After the liquid-covered development, rinsing was performed with pure water for 20 seconds in a rotary shower, and further, water rinsing was performed with pure water for 20 seconds. Then, water droplets remaining on the wafer were blown off with high-pressure air, the substrate was naturally dried, and a square pixel pattern was formed by heat treatment on a hot plate with a surface temperature of 230° C. for 5 minutes. The film thickness of the green pattern after the heat treatment was 0.80 μm.

Next, a red coloring pixel layer was formed using the red photosensitive coloring composition (RR-12) in the same manner as the green coloring pixel layer, and a blue coloring picture was formed using the blue photosensitive coloring composition (RB-100). A pixel layer was formed to obtain a color filter for a solid-state imaging element. The color filter for solid-state imaging elements produced as described above has very good red spectral characteristics and excellent heat resistance, and therefore, the color filters for solid-state imaging elements using the color filter for solid-state imaging elements are particularly excellent in reproducibility of skin color.

without

without

Claims (7)

A pigment composition for color filters, comprising a diketopyrrolopyrrole pigment (A1) represented by the general formula (1) and a diketopyrrolopyrrole pigment (A2) represented by the general formula (2), wherein The mass ratio of the diketopyrrolopyrrole pigment (A1) to the diketopyrrolopyrrole pigment (A2) is 99.9:0.1-90.0:10.0; general formula (1)

In general formula (1), X represents a halogen atom, general formula (2)

In the general formula (2), Y and Z each independently represent a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted phenyl group; wherein, Y and At least one of Z is an alkyl group having 3 to 18 carbon atoms. The pigment composition for color filters according to claim 1, further comprising a pigment derivative. A coloring composition for a color filter, comprising a colorant, a resin and a solvent, and the colorant contains the pigment composition for a color filter according to claim 1 or claim 2. The coloring composition for color filters according to claim 3, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. A color filter comprising a filter segment formed of the coloring composition for a color filter as claimed in claim 3 or claim 4. A liquid crystal display device comprising the color filter according to claim 5. A solid-state imaging element comprising the color filter according to claim 5.