JP2020038334A - Coloring composition, photosensitive coloring composition, color filter, and color liquid crystal display device - Google Patents

Abstract

To provide a coloring composition with superior viscosity stability, a photosensitive coloring composition with high sensitivity, fast development speed, and superior viscosity stability, a color filter produced using such photosensitive coloring composition, and a color liquid crystal display device.SOLUTION: The above challenge is cleared by providing a coloring composition comprising a pigment (A), pigment derivative (B), resin dispersant (C), and binder resin (D). The pigment (A) is at least one pigment selected from a group consisting of aluminum phthalocyanine pigments, zinc phthalocyanine pigments, halogenated diketopyrrolopyrrole pigments, and quinophthalone pigments, and has an average primary particle diameter of 10-80 nm. The resin dispersant (C) comprises an acidic resin dispersant described in one of (C1) through (C4) below. The coloring composition has an average dispersed particle diameter of 30-200 nm.SELECTED DRAWING: Figure 1

Description

  The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, a coloring composition used for manufacturing a color filter used for electronic paper and the like, and a photosensitive coloring composition. Also, the present invention relates to a color filter including a filter segment formed using the same, and a color liquid crystal display device.

The color filter is formed by arranging two or more types of fine strip-shaped filter segments having different hues in parallel (in a stripe shape) or crossing each other on a transparent substrate such as a glass substrate. Are arranged so that two or more types of fine filter segments different from each other are sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundred microns, and are arranged in a predetermined arrangement for each hue.
At present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment excellent in various resistances such as light resistance and heat resistance as a coloring material has become mainstream. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and thereafter, if necessary, a treatment such as heating is performed. Thereby, the filter segment pattern of the first color is obtained. By performing the same operation as above, a filter segment pattern of another color is formed, and a color filter is completed.

  In recent years, high color reproduction of displays has become an important trend. Higher color reproduction of displays has been focused on improving the color reproducibility of the backlight, but it is necessary to use very dark colors for the color filters in order to improve the color reproducibility. In such a case, in the exposure step of forming the pattern of the color filter, the amount of light reaching the bottom of the coating film is weak, so that photocuring tends to be insufficient, and a problem that a pattern having a desired shape cannot be obtained occurs. I do.

  Specifically, the size of the pattern obtained in the color filter manufacturing process, when the exposure amount in the exposure process is varied, the photosensitive colored composition is required to have a dimensional stability that can be accommodated within a certain degree of variation. In a photosensitive coloring composition which realizes high color reproduction, such dimensional stability tends to be deteriorated. Similarly, in a photosensitive coloring composition that achieves high color reproduction, the linearity of the pattern tends to be deteriorated.

  Various methods have been studied so far to solve these problems. For example, in Patent Document 1, dimensional stability is ensured by adding a polymer having a specific structure to a photosensitive composition. In Patent Document 2, a pattern shape and dimensional stability are realized by providing an anchor layer on a substrate. In Patent Literature 3, stability of a pattern dimension at a low exposure amount is realized by adding a polymer having a specific structure to a photosensitive composition. In Patent Document 4, dimensional stability is achieved by using a polymerization initiator having a specific structure. In Patent Document 5, dimensional stability against development is ensured by using a thiol-based compound. However, high dimensional stability and linearity required for color filters have not been sufficiently achieved today, and further improvements are needed.

JP 2013-254407 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A

  The present invention provides a colored composition having excellent viscosity stability, a photosensitive composition having high sensitivity, a high developing speed, and excellent viscosity stability, and a color filter formed using the photosensitive colored composition. And a color liquid crystal display device.

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

[1] A coloring composition containing a pigment (A), a dye derivative (B), a resin-type dispersant (C), and a binder resin (D), wherein the pigment (A) is an aluminum phthalocyanine pigment or a zinc phthalocyanine. Pigment, halogenated diketopyrrolopyrrole pigment, and at least one selected from the group consisting of quinophthalone pigments, the average primary particle diameter of which is 10 to 80 nm, and the resin type dispersant (C) is (C1) A coloring composition comprising the acidic resinous dispersant represented by any one of (C4) to (C4), wherein the coloring composition has an average dispersed particle size of 30 to 200 nm.
(C1): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound. Part A, a vinyl polymer obtained by radical polymerization of one or more ethylenically unsaturated monomers selected from the group consisting of an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group A dispersant comprising a part B, wherein the vinyl polymer part B has a (meth) acryloyl group.
(C2): a dispersant represented by the following general formula (1).
Formula _{(1) (HOOC-) m -R} 1 - (- COO - [- R 3 -COO-] n -R 2) t
Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
(C3): a dispersant containing, as a copolymerization component, an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group, and another ethylenically unsaturated monomer.
(C4): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound A dispersant comprising a part A and a vinyl polymer part B obtained by radical polymerization of one or more ethylenically unsaturated monomers.

[2] The colored composition according to [1], further comprising a dye.

[3] A photosensitive coloring composition comprising the coloring composition according to [1] and [2], a polymerizable compound (F), and a photopolymerization initiator (G).

A color filter formed using the photosensitive coloring composition according to [3].

  A liquid crystal display device comprising the color filter according to [4].

  The present invention provides a colored composition having excellent viscosity stability, a photosensitive composition having high sensitivity, a high developing speed, and excellent viscosity stability, and thus provides a high-quality color filter and a color liquid crystal display device. it can.

FIG. 1 is a schematic sectional view of the liquid crystal display device.

Hereinafter, each component of the photosensitive coloring composition of the present invention will be described.
In addition, in this application, especially described as "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide". Unless otherwise specified, "acryloyl and / or methacryloyl", "acryl and / or methacryl", "acrylic and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Shall be represented.
Further, “CI” described in this specification means a color index (CI).

The present invention is a coloring composition containing a pigment (A), a dye derivative (B), a resin-type dispersant (C), and a binder resin (D), wherein the pigment (A) is an aluminum phthalocyanine pigment, zinc It contains a pigment having an average primary particle diameter of 10 to 80 nm selected from the group consisting of phthalocyanine pigments, halogenated diketopyrrolopyrrole pigments, and quinophthalone pigments, and the resin-type dispersant (C) has the following (C1) To (C4), characterized by having an average dispersed particle diameter of 30 to 200 nm.
(C1): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound. Part A, a vinyl polymer obtained by radical polymerization of one or more ethylenically unsaturated monomers selected from the group consisting of an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group A dispersant comprising a part B, wherein the vinyl polymer part B has a (meth) acryloyl group.
(C2): a dispersant represented by the following general formula (1).
Formula _{(1) (HOOC-) m -R} 1 - (- COO - [- R 3 -COO-] n -R 2) t
Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
(C3): a dispersant containing, as a copolymerization component, an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group, and another ethylenically unsaturated monomer.
(C4): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound A dispersant comprising a part A and a vinyl polymer part B obtained by radical polymerization of one or more ethylenically unsaturated monomers.

Aluminum phthalocyanine pigments, zinc phthalocyanine pigments, halogenated diketopyrrolopyrrole pigments, and pigments having an average primary particle diameter of 10 to 80 nm selected from the group consisting of quinophthalone pigments, the acidic resin type dispersion of the specific structure described above By dispersing with an agent, the average dispersed particle diameter is in the range of 30 to 200 nm, and a colored composition having excellent viscosity and storage stability can be obtained.

<Pigment (A)>
The coloring composition of the present invention is a coloring composition containing a pigment (A), a pigment derivative (B), a resin-type dispersant (C), and a binder resin (D), wherein the pigment (A) is aluminum. A pigment having an average primary particle diameter of 10 to 80 nm selected from the group consisting of phthalocyanine pigments, zinc phthalocyanine pigments, diketopyrrolopyrrole halogenated pigments, and quinophthalone pigments.

(Other pigments)
As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more. As the pigment, a pigment having a high coloring property and a high heat resistance, particularly a pigment having a high thermal decomposition resistance is preferable, and an organic pigment is usually used. Hereinafter, specific examples of the organic pigments that can be used in the coloring composition for a color filter are shown by color index numbers.

Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291 and the like. Also, diketopyrrolopyrrole pigments described in JP-A-2011-523433 and JP-A-2017-138417, or azo pigments described in JP-A-2014-112527, and azo pigments described in JP-A-2013-161046 Pigments and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291 and more preferably C.I. I. Pigment Red 177, 254, 291.

  The red coloring composition includes C.I. I. An orange pigment such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and / or a yellow pigment described later may be used in combination.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Further, a purple pigment described later may be used in combination with the blue coloring composition.

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

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and JP-A-2012-155231, JP-A-2
Examples of the pigment include pigments described in 016-153481, but are not particularly limited thereto. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62 or 63.
The green coloring composition may be used in combination with a yellow pigment described below.

  For the yellow pigment, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 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, 82,185,187,188,192,193,194,196,198,199,213,214,231, also can be mentioned pigments described in JP-A-2012-226110. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

The cyan coloring composition for forming the cyan filter segment includes, for example, C.I. I. Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 can be used alone or in combination.

The magenta coloring composition for forming the magenta color filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C.I. I. A violet pigment and a red pigment such as CI Pigment Red 144, 146, 177, 169, and 81 can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, navy blue, chromium oxide green, cobalt green, amber. And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.

<Other coloring agents>
The photosensitive composition of the present invention may contain a coloring agent such as a dye other than the pigment (A).
<Dye (a)>
As the dye, any of an acid dye, a direct dye, a basic dye, a salt-forming dye, an oil-soluble dye, a disperse dye, a reactive dye, a mordant dye, a vat dye, a sulfur dye and the like can be used. In addition, these derivatives may be in the form of a lake pigment obtained by laking a dye.

Further, an acid dye having an acid group such as sulfonic acid or carboxylic acid, in the case of a direct dye, an inorganic salt of the acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound or the like, or salt formation using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamidation and use as a sulfonamide compound , And is excellent in durability, so that a colored composition having excellent fastness can be obtained, which is preferable.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in a side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with a pigment, and furthermore, a basic dye and an organic sulfonic acid, an organic sulfuric acid, and a fluorine group-containing phosphorus which are counter components serving as counter ions. It is possible to use an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt formed with an acid dye. More preferred.

  When the dye skeleton has a polymerizable unsaturated group, a dye having excellent resistance can be obtained, which is preferable.

  Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, and quinone dyes (benzoquinone dyes, naphthoquinone dyes, and anthraquinone dyes). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes Pigment structures derived from dyes selected from perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof can be given. .

  Among these dye structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and squarylium, from the viewpoint of color characteristics such as hue, color separation, and color unevenness. Dyes, quinophthalone dyes, phthalocyanine dyes, dye structures derived from dyes selected from subphthalocyanine dyes are preferred, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A dye structure derived from a dye selected from system dyes is more preferable. Specific dye compounds capable of forming a dye structure are described in “New Edition Dye Handbook” (edited by The Society of Synthetic Organic Chemistry, Maruzen, 1970), “Color Index” (The Society of Dysers and colors), “Dye Handbook” (Okawara et al.) (Kodansha, 1986).

<Refinement of pigment>
The method for pulverizing the pigment used in the photosensitive coloring composition of the present invention is not particularly limited.For example, wet milling, dry milling, and dissolution precipitation can be used. Fineness can be achieved by a salt milling treatment or the like by a kneader method, which is a kind of grinding. It is preferable that the pigment has an average primary particle diameter of 10 to 80 nm determined by TEM (transmission electron microscope). If it is smaller than 10 nm, dispersion in an organic solvent becomes difficult, and if it is larger than 80 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferred average primary particle size is in the range of 15 to 70 nm.

Salt milling treatment is a batch or continuous method of mixing a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent with a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like. This is a process of mechanically kneading while heating using a kneader, and then removing the water-soluble inorganic salt and the water-soluble organic solvent by washing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

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

  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 dissolves (mixes) with water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, 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- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

  When the pigment is subjected to the salt milling treatment, a resin may be added as necessary. The type of the resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Dye derivative (B)>
The dye derivative (B) is added to the photosensitive coloring composition used in the present invention.

As the dye derivative used in the present invention, a known dye derivative having an organic dye residue having an acidic group, a basic group, a neutral group, or the like can be used. For example, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group and the like, amine salts thereof, compounds having a sulfonamide group and a basic substituent such as a tertiary amino group at a terminal, a phenyl group and a phthalimide Compounds having a neutral substituent such as an alkyl group are exemplified. Since the resin dispersant used in combination has an acidic group, a dye derivative having a basic group is preferred. When using an acidic derivative, it is preferable to use a combination of a basic resin and an acidic resin-type dispersant.
As organic dyes, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzo Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, sulene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo. Can be

Specifically, examples of the diketopyrrolopyrrole dye derivative include JP-A-2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP2017-156397, and phthalocyanine. JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-5573266, and JP-A-575-266, and anthraquinone-based pigment derivatives include JP-A-63-26467.
No. 4, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325, pamphlet of Japanese Patent Application Publication No. JP-A-48-54128, JP-A-H03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, and JP-A-2011-166662 as a thiazineindigo-based dye derivative JP-A-2007-314785 and JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208 and JP-A-2004 217842, JP-A-2007-314 JP-A-2009-57478 as a benzoisoindole-based dye derivative and JP-A-2003-167112, JP-A-2006-291194, and JP-A-2008-31281 as quinophthalone-based dye derivatives. JP, JP-A-2012-226110, JP-A-2012-208329, JP-A-2014-5439 as naphthol-based dye derivatives, JP-A-2001-172520, and JP-A-2001-172520 as azo-based dye derivatives JP-A-2012-172092, as an acidic substituent, JP-A-2004-307854, and as a basic substituent, JP-A-2002-201377, JP-A-2003-171594, and JP-A-2005-181383. And JP-A-2005-213404. Include the dyes known derivatives of. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. The compound having a substituent such as a sex group has the same meaning as the dye derivative.

These dye derivatives can be used alone or in combination of two or more.
More specifically, the following dye derivatives are preferred.

[Diketopyrrolopyrrole dye derivative]

[Phthalocyanine dye derivative]

General formula (103)

[Anthraquinone dye derivative]

[Quinacridone dye derivative]

General formula (108)

[Dioxazine dye derivative]

[Thiazine indigo dye derivative]

General formula (111)

[Triazine dye derivative]


General formula (112)

[Benzoisoindole dye derivative]


General formula (113)

[Quinophthalone dye derivative]

[Naphthol dye derivative]


General formula (129)

[Azo dye derivative]

General formula (133)

In the general formulas (101) to (112), (114) to (128), and (130) to (133), R _{101 to} R ₁₁₇ , R ₁₂₉ , R ₁₃₀ , and R _{141 to} R ₁₄₅ each independently represent hydrogen. Atom, hydroxyl group, alkyl group which may have a substituent, alkoxy group which may have a substituent, phthalimidoalkyl group which may have a substituent, acyl group which may have a substituent, amino A group, a sulfo group, a carboxyl group, a phosphate group, a halogen group, or a group represented by any of the general formulas (150) to (155), (158), or (159). m and n each independently represent a positive integer. However, when one molecule has a plurality of substituents, one or more is a substituent other than a hydrogen atom. When only one substituent is present in one molecule, it is a substituent other than a hydrogen atom.

In Formula (113), R ₁₁₈ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, —SO ₂ R ₁₇₇ , or —NR ₁₇₈ R ₁₇₉ . Here, R ₁₇₇ is a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and R ₁₇₈ and R ₁₇₉ each independently represent a hydrogen atom represents an alkyl group having 1 to 12 carbon atoms, or a further nitrogen together with the R ₁₇₈ and R _179, a heterocyclic ring which may contain an oxygen or sulfur atom.
R ₁₁₉ represents a hydrogen atom, an alkyl group which may have a substituent, or an acyl group which may have a substituent.
R ₁₂₀ , R ₁₂₁ and R _{123 to} R ₁₂₈ each independently represent a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, a halogen atom, a cyano group, or a substituent. Or NR ₁₈₀ R ₁₈₁ . However, R ₁₈₀ and R ₁₈₁ may be, independently of each other, a hydrogen atom, an alkyl group which may have a substituent, or a further nitrogen, oxygen or sulfur atom integrated with R ₁₈₀ and R _181. Represents a good heterocycle.
R ₁₂₂ represents a hydrogen atom, an alkyl group which may have a substituent, an acyl group which may have a substituent, or a group represented by any of the general formulas (150) to (155).

In the general formula (129), R _{131 to} R ₁₄₀ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, or a group represented by the general formula (150), (153), or (159). Represents a group to be formed. Adjacent groups of R _{131 to} R ₁₄₀ may be bonded by a —NHCONH— group to form a benzimidazolone ring. At least one of R _{131 to} R ₁₄₀ is a group represented by the general formula (150), (153) or (159).

In the general formulas (150) to (155),
X ₁ is a direct bond, -SO2 -, - CO -, - CH2 -, - CH2NHCOCH2 -, - CONHC 6 H 4 CO-, or -CONHC ₆ H ₄ - represents a.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an arylene group which may have a substituent, or a heteroaromatic ring which may have a substituent, and these groups are represented by —NR ₁₇₀ —, —O—, and —SO ₂ — Or CO— may be mutually connected by a divalent linking group selected from —CO—.
Y ₃ is a direct _{bond, -NR 170} - represents a or -O-.
o represents an integer of 0 to 20.
M ₁ represents a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom, and an iron atom.
M ₂ represents a hydrogen atom, calcium atom, a barium atom, strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _{M 2.}
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a combination of R ₁₅₀ and R ₁₅₁ . Represents a heterocyclic ring which may have a substituent and further contains a nitrogen, oxygen or sulfur atom.
R _{152 to} R ₁₅₆ and R _{159 to} R ₁₆₂ each independently may have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O— (CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ ,
Represents —Cl, —F or Y ₃ —Y ₂ —Y ₁ —Q, and _{one of} R ₁₅₇ and R ₁₅₈ is a group represented by the following general formula (156) or (157), —O— ( CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ .
R ₁₇₀ represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent.
R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R _{172 to} R ₁₇₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent which may have a substituent. It represents a good alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

General formula (156)

In General Formula (156), Z ₁ represents —NR ₁₇₀ —, —CONH—, or —O—, and Z ₂ represents an alkylene group optionally having a substituent or an alkenylene group optionally having a substituent. represents an arylene group which may have a substituent, these _{groups, -NR 170 -, - O -} , - SO 2 - or a divalent linking group selected from CO- be coupled to each other Is also good. _{However, R 170} has the same meaning as _{R 170} in formula (150) - (155).
R ₁₅₀ and R ₁₅₁ are each independently an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or R ₁₅₀ and R ₁₅₁ Represents a heterocyclic ring which may have a substituent and further contains a nitrogen, oxygen or sulfur atom.

General formula (157)

In the general formula (157), Z ₃ represents a single bond connecting a triazine ring and a nitrogen atom, —NR ₁₇₅ —, —NR ₁₇₅ —Z ₄ —CO—, —NR ₁₇₅ —Z ₄ —CONR ₁₇₆ —, and —NR _{175.
-Z 4 -SO 2 -, - NR} 175 -Z 4 - SO 2 NR 176 -, - O-Z 4 -CO-,
_{-O-Z 4 -CONR 175 -,} - O-Z 4 -SO 2 -, or _{O-Z 4 -SO 2 NR 175} - _{represents, R 175} and _{R 176} each independently represent a hydrogen atom, a substituent Represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent or a phenyl group which may have a substituent, and Z ₄ represents an alkylene group which may have a substituent, a substituent Represents an alkenylene group which may have or an arylene group which may have a substituent.
R _{152 to} R ₁₅₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene. Represents a group.

General formula (158)

General formula (159)

In the general formula _(159), X _{2 is, -SO 2 -, - CO -} , - NH -, - SO 2 NH -, - NHSO 2 -, - represents CONH- or _{-NHCO-, R} 163 ~R ₁₆₇ Is each independently a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphate group or a group represented by any of the general formulas (150) to (155).

As the alkyl group which may have a substituent, a linear alkyl group having 1 to 20 carbon atoms is preferable as the alkyl group, and a hydrogen or halogen group is preferable as the substituent which may have.
The phthalimidoalkyl group which may have a substituent is preferably an alkyl group having 1 to 3 carbon atoms as an alkyl group, and a hydrogen or halogen group is preferable as an optionally substituted substituent.
As the acyl group which may have a substituent, an alkyl group is preferably an acyl group having 1 to 10 carbon atoms, and a substituent which may be possessed is preferably hydrogen or a halogen group.
As the optionally substituted alkoxy group, an alkyl group is preferably a straight-chain alkoxy group having 1 to 5 carbon atoms, and the optionally substituted substituent is preferably hydrogen or a halogen group. The alkenyl group or alkenylene group which may have a substituent is preferably hydrogen or a linear alkyl group having 1 to 10 carbon atoms.
The optionally substituted phenyl group is preferably a hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group.
The arylene group which may have a substituent is preferably a hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group which may have a substituent.
The heterocyclic ring which may have a substituent is preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, or tetrahydrothiopyran as the heterocyclic ring. And a linear alkyl group or alkoxy group having 1 to 10 carbon atoms.
The heteroaromatic ring which may have a substituent is preferably pyrrole, pyridine, furan or thiophene as the heteroaromatic ring, and hydrogen, a halogen group or a straight chain having 1 to 10 carbon atoms as the substituent which may be possessed. Alkyl groups and alkoxy groups are preferred.

  In particular, diketopyrrolopyrrole-based dye derivatives represented by the general formulas (101) and (102), which have substituents represented by the general formulas (150), (151), and (155), preferable.

  The dye derivative is preferably added in an amount of 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment.

  By adding a pigment derivative to the pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the pigment derivative is adsorbed on the pigment surface and the pigment derivative is not added. In comparison, the primary particles of the pigment can be made finer.

By adding a pigment derivative to the pigment and performing dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the pigment derivative is adsorbed on the pigment surface and the pigment surface is polar and adsorbs the resin type dispersant. Is promoted, the compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and the dispersion stability and viscosity stability over time when formed into a colored composition or a colored curable composition are improved. I do. In addition, since the compatibility is improved, the colored curable composition is coated with a glass substrate or the like, and has excellent stability over time, and the waiting time from application of the colored curable composition to exposure (PCD: Post)
The stability and characteristic dependence of the pattern shape, etc., on the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and line width sensitivity stability are improved. In addition, since the pigment surface is adsorbed and covered with the pigment derivative and the resin-type dispersant, the precipitation of crystals due to aggregation and sublimation of the pigment when the coating film is heated and baked can be suppressed. Further, variations in development time and development residues are also suppressed.

<Resin type dispersant (C)>

The resin type dispersant (C) used in the photosensitive coloring composition of the present invention is an acidic resin type dispersant represented by any of the following (C1) to (C4).
(C1): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound. Part A, a vinyl polymer obtained by radical polymerization of one or more ethylenically unsaturated monomers selected from the group consisting of an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group A dispersant comprising a part B, wherein the vinyl polymer part B has a (meth) acryloyl group.
(C2): a dispersant represented by the following general formula (1).
Formula _{(1) (HOOC-) m -R} 1 - (- COO - [- R 3 -COO-] n -R 2) t
Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
(C3): a dispersant containing, as a copolymerization component, an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group, and another ethylenically unsaturated monomer.
(C4): a polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound A dispersant (C4-1) comprising part A and a vinyl polymer part B obtained by radical polymerization of one or more ethylenically unsaturated monomers.

The patent publication numbers relating to the dispersants (C1) to (C4) are described below.
(Dispersant of (C1)) Dispersant described in JP-A-2011-157416.

(Dispersant of (C2)) Dispersant described in JP-A-2007-140487.

(Dispersant of (C3)) Dispersants described in JP-A-2003-253078 and JP-A-2008-161737.
(Dispersant of (C4)) It is a dispersant (A) described in JP-A-2009-185277, and preferably further contains a vinyl resin having a tertiary amino group (B) described in the same.

(Other resin type dispersants)
Known resin-type dispersants other than those described above may be used in the photosensitive coloring composition of the present invention. The resin-type dispersant (C) has a colorant affinity site having a property of adsorbing to the additive colorant and a site compatible with the colorant carrier, and adsorbs to the additive colorant to absorb the colorant carrier. Any substance can be used as long as it has a function of stabilizing dispersion in urethane. Specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, and polycarboxylic acid ( Part) Amine salts, ammonium polycarboxylates, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters and their modified products, free from poly (lower alkyleneimine) Oil-based dispersants such as amides and salts thereof formed by reaction with a polyester having a carboxyl group of (meth) acrylic acid-styrene Water-soluble resin or water-soluble polymer compound such as polymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified Polyacrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used, and these can be used alone or in combination of two or more.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chem Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, BYK-LPN21116, BYK-LPN21324, or Lactimon, Lactimon-WS or Bykumen, etc. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Brisol EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055 manufactured by BASF, such as 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500. , 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB821, PB822, PB824, and the like. The resin dispersant used in the present invention is a resin dispersant having a carboxyl group.

  The resin-type dispersant is preferably used in an amount of about 3 to 200% by weight, and more preferably about 5 to 100% by weight, from the viewpoint of film formability.

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

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

<Thermoplastic resin>
As the thermoplastic resin that can be used as the binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE
, LDPE), polybutadiene, and polyimide resin.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include a resin having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the resin include an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (Anhydrous) maleic acid copolymer and the like. Above all, an acrylic resin having an acidic group, and at least one resin selected from styrene / styrene sulfonic acid copolymers, particularly an alkali-soluble resin having an acidic group and / or a hydroxyl group, have developability, heat resistance, and transparency. Since it is high, it is preferably used.

<Alkali-soluble resin>
The coloring composition of the present invention preferably contains an alkali-soluble resin from the viewpoints of developability, heat resistance, and transparency. This is for imparting development solubility in an alkaline development step at the time of producing a color filter and has an acid group and / or a hydroxyl group. In order to further improve photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

<Alkali-soluble resin having ethylenically unsaturated double bond>
The alkali-soluble resin contained in the coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond is introduced by the following methods (i), (ii) and (iii), the resin becomes 3 when exposed to active energy rays to form a coating film. The dimensional cross-linking increases the cross-link density and improves the chemical resistance.

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers may be used. The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction. There is a way to introduce it.

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

  Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl (meth) acrylic acid, alkoxyl, halogen, nitro and cyano-substituted products. Monocarboxylic acids may be used, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. I don't care. Increasing the number of carboxyl groups, etc., if necessary, using a tricarboxylic anhydride such as trimellitic anhydride, or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining anhydride Hydrolysis of the group can also be performed. When tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

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

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and a monomer of another unsaturated monobasic acid having a carboxyl group or by copolymerizing with another monomer. There is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol Examples include hydroxyalkyl methacrylates such as mono (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Also, polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like has been added can also be used. 2-hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferred from the viewpoint of suppressing coating film foreign matter, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. And glycerol mono (meth) acrylate is more preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. However, the present invention is not limited thereto, and two or more kinds can be used in combination.

The following are examples of monomers constituting the alkali-soluble resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyether Glycol (meth) acrylate of (meth) acrylates,
Alternatively, a (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or (meth) such as acryloylmorpholine Acrylamides Styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, and fatty acid vinyls such as vinyl propionate And the like.

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

General formula (2)

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

  Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.

Also, a hydroxyl group-containing ethylenically unsaturated monomer can be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-
Examples thereof include hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like has been added.

Further, a phosphoric ester group-containing ethylenically unsaturated monomer can also be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include, for example, monomers obtained by reacting a hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

[Method (iii)]
In the method (iii), an unsaturated ethylenic double bond and the like can be introduced by copolymerizing a side chain type cyclic ether-containing monomer with one or more other monomers.
Examples of the side chain type cyclic ether-containing monomer include at least one selected from the group consisting of a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, and a lactone skeleton.
It is an unsaturated compound containing two skeletons.
Examples of the tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and (meth) acrylic acid tetrahydrofuran-3-yl ester;
As the furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-en-2-one, 1-furan -2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1-ene -3-one, acrylic acid 2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one and the like;
Examples of the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. -2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like;
As the pyran skeleton, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6-oxo-7-octenyl) -6 -Methyl-2-pyrone and the like;
As the lactone skeleton, 2-propenoic acid 2-methyl-tetrahydro-2-oxo-3-furanyl ester, 2-propenoic acid 2-methyl-7-oxo-6-oxabicyclo [3.2.1] oct-2-yl Yl ester, 2-methyl-2-propenoic acid 2-methyl-hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-7-yl ester, 2-propenoic acid 2-methyl-tetrahydro-2-oxo- 2H-pyran-3-yl ester, 2-propenoic acid (tetrahydro-5-oxo-2-furanyl) methyl ester, 2-propenoic acid hexahydro-2-oxo-2,6-methanofuro [3,2-b]- 6-yl ester, 2-methyl-2-propenoic acid 2- (tetrahydro-5-oxo-3-furanyl) ethyl ester, 2-propenoic acid 2-meth Le-decahydro-8-oxo-5,9-methano-2H-furo [3,4-g] -1-benzopyran-2-yl ester, 2-methyl-2-propenoic acid 2-[(hexahydro-2- Oxo-3,5-methano-2H-cyclopenta [b] furan-6-yl) oxy] ethyl ester, 3-oxo-3-[(tetrahydro-2-oxo-3-furanyl) oxy] propyl 2-propenoate And 2-propenoic acid 2-methyl-2-oxy-1-oxaspiro [4.5] dec-8-yl ester. Of these, tetrahydrofurfuryl (meth) acrylate is preferable in terms of coloring, pigment dispersibility, and availability. These side chain type cyclic ether-containing monomers may be used alone or in combination of two or more.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. By synthesizing using at least one kind of carboxyl group-containing ethylenically unsaturated monomer and at least one other ethylenically unsaturated monomer and not giving an ethylenically unsaturated bond to a side chain, ethylene An alkali-soluble resin having no unsaturated unsaturated double bond can be obtained.

  The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is from 2,000 to 40,000, preferably from 3,000 to 300,00, and more preferably from 4,000 to impart alkali development solubility. It is more preferably from 20,000 to 20,000. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is reduced, and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development is reduced, residues are generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg / g), preferably from 70 to 180, more preferably from 90 to 170 in order to impart alkali development solubility. Range. If the acid value is less than 50, the solubility in alkali development decreases, residues are generated, and the linearity of the pattern deteriorates. If it exceeds 200, the adhesion to the substrate will be reduced, and the exposure pattern will not remain easily.

<Thermosetting compound (E)>
In the present invention, a thermosetting compound (E) can be further contained in combination with a thermoplastic resin as a binder resin. When producing a color filter using the color composition for a color filter of the present invention, by containing a thermosetting compound, the reaction during firing of the filter segment increases the crosslink density of the coating film, so that the heat resistance of the filter segment is increased. The effect is obtained that pigment aggregation during firing of the filter segment is suppressed, and the contrast ratio is improved.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound, but the present invention is not limited thereto. It is not done. In the coloring composition for a color filter of the present invention, an epoxy compound and an oxetane compound are preferably used.

(Epoxy compound (E-1))
The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Phenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol) Polycondensates with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols with various aldehydes, alcohols Glycidyl Glycidyl ether-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin, etc. It is not limited. These may be used alone or in combination of two or more.

As commercially available products, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (and above) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L
(Trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), JER
157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (the above are trade names, manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (the above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (the above trade names; manufactured by Daicel Chemical Industries, Ltd.), TTA3150 (manufactured by Kusumoto Kasei Co., Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (the above are products) Name: Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPI -S (manufactured by Nissan Chemical Industries, Ltd.), and the like.
And the like, but are not limited to these.

  The compounding amount of the epoxy compound is preferably from 0.5 to 300 parts by weight, more preferably from 1.0 to 50 parts by weight, based on 100 parts by weight of the coloring agent. If the amount is less than 0.5 part by weight, the effect of improving the contrast ratio and the heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

(Oxetane compound (E-2))
An oxetane compound is preferably added to the photosensitive coloring composition of the present invention. As the oxetane compound, a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include a compound having an oxetane group that is monofunctional, a compound having an oxetane group that is bifunctional, and a compound having an oxetane group that is bifunctional or more.

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

When the oxetane group is bifunctional, examples thereof include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-E Tyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycosebis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl -3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl -3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bis Enol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Oxetane groups having two or more functional groups include:
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, oxo Resin (e.g., Patent No. 3,783,462 No. oxetane-modified phenol novolak resin according) containing Tan group or above, such as OXE-30 (meth) polymers obtained by the acrylic monomer by radical polymerization. Such a polymer can be obtained by using a known polymerization method.

  The content of the oxetane compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass based on 100% by mass of the solid content of the coloring composition. It is preferable that the content of the oxetane compound is in the above range, since an excellent coating film having good water stain and high chemical resistance can be obtained.

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

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

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

(Curing agent)
In addition, the coloring composition for a color filter of the present invention may contain a curing agent (curing accelerator) or the like as needed in order to assist the curing of the thermosetting compound. As a curing agent, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, and the like are effective, but are not particularly limited thereto, and can react with a thermosetting compound. Any curing agent may be used. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, 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 (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 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) and the like. . These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the thermosetting compound.

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

  Examples of monomers and oligomers which are cured by ultraviolet light or heat to produce a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylol Lopan PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate (Meth) acrylates of methylolated melamine, epoxy (meth) acrylates, urethane acrylates and other acrylic and methacrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Examples include vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and the like, but are not necessarily limited thereto.

  As these commercially available products, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO- manufactured by Nippon Kayaku Co., Ltd. 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Alonix M-303, M manufactured by Toagosei Co., Ltd. -305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403 , M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, screws manufactured by Osaka Organic Co., Ltd. Over preparative # 310HP, # 335HP, # 700, # 295, # 330, # 360, # GPT, # 400, # 405, can be preferably used by Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300 and the like.

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

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

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

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

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

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  As these commercially available products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Shin-Nakamura Chemical Co., Ltd. manufactured by Kyoeisha Chemical Co., Ltd. UA-160TM, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry, and the like can be suitably used.

  The above photopolymerizable monomers can be used alone or as a mixture of two or more kinds at an optional ratio as needed.

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

<Photopolymerization initiator (G)>
The photosensitive composition of the present invention contains a photopolymerization initiator (G). By containing the photopolymerization initiator (G), the composition can be cured by irradiation with ultraviolet rays, and a filter segment can be formed by photolithography. It is preferable to add a photopolymerization initiator (G) to prepare in the form of a solvent development type or alkali development type photosensitive composition.

Examples of the photopolymerization initiator (G) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) Phenyl] -2- (phenylmethyl) -1-butanone or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin-based compounds such as propyl ether or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, or 3, Benzophenone-based compounds such as 3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4 -Thioxanthone compounds such as -diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2 Triazine compounds such as 1,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- O-benzoyl oxime)] or an oxime ester compound such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) A phosphine compound such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. Quinone compounds; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.
One of these photopolymerization initiators can be used alone, or two or more of them can be used in an optional ratio as needed.

  As commercial products, all acetophenone-based compounds are manufactured by IGM Resins and manufactured by "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), "Omnirad 369E "(2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone)," Omnirad 379EG "(2- (dimethylamino) -2- [ (4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) and phosphine-based compounds manufactured by IGM Resins, Inc., “Omnirad 819” (bis (2,4,4 6-trimethylbenzoyl) -phenylphosphine oxide), "Omnirad TPO" Sulfonyl-2,4,6-trimethyl benzoyl phosphine oxide), and the like.

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

(Oxime ester compound)
The oxime ester-based compound absorbs ultraviolet rays to cause cleavage of the N—O bond of the oxime, thereby generating an iminyl radical and an alkyloxy radical. These radicals are further decomposed to generate highly active radicals, so that a pattern can be formed with a small exposure dose. When the colorant concentration of the photosensitive coloring composition is high, the UV transmittance of the coating film is low and the degree of curing of the coating film may be low, but the oxime ester compound is preferably used because it has a high quantum efficiency. You. More preferred are oxime ester-based photopolymerization initiators represented by the general formula (3).

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

In the general formula (3),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent) And the like.

Examples of the alkenyl group which may have a substituent for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. May have a carbon double bond, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 1-pentenyl group. , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

Examples of the alkyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms, and A linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by at least -O- is exemplified. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and octyl. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —CH ₂ —O—CH ₃ and —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 from a _{8), -} (CH 2 is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 - CH ₃ , —CH ₂ —CH— (OCH ₃ ) _{2 and the} like can be mentioned, but it is not limited to these.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include the following, but are not limited thereto. It is not something to be done.

Examples of the alkyloxy group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. A straight-chain, branched-chain, monocyclic or condensed polycyclic alkyloxy group optionally interrupted by one or more —O— is mentioned. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy, ethyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy, tert-pentyloxy, tert-octyloxy, neopentyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, norbornyloxy, boronyl Alkoxy group, may be mentioned 4-decyl cyclohexyl group and the like, but is not limited thereto. Further, linear interrupted by one or more -O- optionally a 2 to 18 carbon atoms, and specific examples of the branched alkyl _{group, -O-CH 2 -O-CH} 3, _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3, -O-CH 2 -CH- (OCH 3) but ₂ and the like, but is not limited thereto.

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

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

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

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

Examples of the optionally substituted heterocyclic oxy group for Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples thereof include a 2-furanyloxy group, a 2-thienyloxy group, a 2-indolyloxy group, a 3-indolyloxy group, a 2-benzofuryloxy group, a 2-benzothienyloxy group, and a 2-carbazolyl group. Examples include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group. , Ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, Examples include, but are not limited to, naphthylthio, 9-anthrylthio, 9-phenanthrylthio, and the like.

The alkylsulfinyl group which may have a substituent in Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group and the like. But are not limited to these.

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

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Examples include, but are not limited to:

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

Examples of the acyl group which may have a substituent in Y ¹ include a hydrogen atom or a carbonyl group having a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms, A carbonyl group substituted with an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group having a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms bonded thereto, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a carbonyl group having a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, and specific examples thereof include formyl. Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, Thearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl Group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl Group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxy Carbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl Although a group etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group and the like. No.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

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

  Examples of the arylamino group include an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, Examples include a biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like, but are not limited thereto.

Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, an N-phenyl-2-naphthylamino group, and the like.

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

Examples of the phosphinoyl group which may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, and a dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, but are not limited thereto. It is not done.

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

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- A methylphenylsulfamoyl group, an N-2-chlorophenylsulfamoyl group, an N-2-methoxyphenylsulfamoyl group, an N-2-isopropoxyphenylsulfamoyl group, an N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group, and the like. However, the present invention is not limited to this.

An alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, which may have a substituent for Y ² ;
The arylsulfanyl group, the alkylsulfinyl group, the arylsulfinyl group, the alkylsulfonyl group, the arylsulfonyl group, the acyloxy group, and the amino group may have an alkenyl group which may have a substituent in R1 described above, Alkyl group, an alkyloxy group optionally having a substituent, an aryl group optionally having a substituent, an aryloxy group optionally having a substituent, and a heterocyclic ring optionally having a substituent Group, heterocyclic oxy group optionally having substituent (s), alkylsulfanyl group optionally having substituent (s), arylsulfanyl group optionally having substituent (s), alkylsulfinyl group optionally having substituent (s) An arylsulfinyl group optionally having a substituent, an alkylsulfonyl group optionally having a substituent, an arylsulfonyl group optionally having a substituent Group, it may acyloxy group which may have a substituent, and is synonymous with an amino group which may have a substituent.

Examples of these substituents in Y ¹ and Y ² include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and a p-tolyloxy group. Aryloxy group such as group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group An acyl group such as a methacryloyl group or a methoxalyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; a methylamino group Alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl Group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, alkyl group such as cyclooctadecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group , Anthryl group, aryl group such as phenanthryl group, furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino Group, nitro group, cyano group, trif Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammonium group, a dimethylsulfonium group, and a triphenylphenacylphosphonium group.
In addition, one or more of these substituents may be present, and a hydrogen atom of these substituents may be further substituted with another substituent.

  Among the oxime ester-based photopolymerization initiators represented by the general formula (3), the oxime ester-based photopolymerization initiators represented by the following general formula (4) or (5) are excellent in sensitivity and more preferable. is there.

[Oxime ester-based photopolymerization initiator represented by the general formula (4)]
General formula (4)

Formula (4) has the general formula (3) Z is -CO- in groups, ^{Y 3} corresponds to the case of Ph-S-Ph- ^group, Y 4 to Y ⁶ is a hydrogen atom or a substituent An alkyl group or an aryl group, which may have, is preferable. The alkyl group which may have a substituent or the aryl group which may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or the aryl group in Y ¹ and Y ² .

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

As Y ⁷ , for example, a fluorine group, a chlorine atom, a bromine atom, a halogen group such as an iodine atom,
Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acetoxy group and propionyloxy Acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, phenylsulfanyl group , Arylsulfanyl groups such as p-tolylsulfanyl group, alkylamino groups such as methylamino group and cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group Arylamino group such as dialkylamino group, phenylamino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group , Naphthyl group, anthryl group, phenanthryl group, aryl group such as benzofuranyl group, heterocyclic group such as furyl group, thienyl group and the like, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p -Toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethylammonium, dimethylsulfonium, triphenylphenacylphosphonium And the like.

More preferably, the substituent for Y ² is a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctadecyl group, or the like.

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

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

General formula (5) corresponds to the case where Y ³ in general formula (3) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y ^{1 It has the same} meaning as the substituent in ² .

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent or a substituent as Y ^2. aryl group, Y ⁷ to Y ¹⁴ as a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent is preferable.

  When Z in the general formula (5) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (5a) is preferable.

"Oxime ester-based photopolymerization initiator represented by general formula (5a)"
General formula (5a)

The general formula (5a) corresponds to the case where Z in the general formula (5) is a direct bond, and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent. Y ⁷ to Y ^10, and ^Y 12 ^{to Y 13} is a hydrogen atom.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ has the same meaning as the substituent for Y ¹ and Y ² , and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

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

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, It is a cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and an alkyl group having 1 to 20 carbon atoms which may further have a substituent, or a methoxy group, an ethoxy group, or a tert-butoxy group is preferable. And the like.

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (5a) include photopolymerization initiators represented by the following chemical formulas (5a-1) to (5a-6).

"Oxime ester photopolymerization initiator represented by general formula (5b)"
When Z in the general formula (5) is a —CO— group, an oxime ester-based photopolymerization initiator represented by the following general formula (5b) is preferable.

General formula (5b)

The general formula (5b) corresponds to a case where Z in the general formula (5) is a monovalent organic group containing a carbazole group and Y ³ is a —CO— group, and a keto-type carbazole group. Is an oxime ester-based photopolymerization initiator. Y ⁷ to Y ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent ^{preferably, Y 14}
Is preferably an aryl group which may have a substituent. As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group is preferable, and a benzoyl group is more preferable.

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (5b) include photopolymerization initiators represented by the following chemical formulas (5b-1) to (5b-4).

Commercial products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IR
GACURE OX-01), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), N- 1919 (made by ADEKA), TRONLYTR-P
BG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like are commercially available. In addition, oximes described in JP-A-2007-21091, JP-A-2009-79619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photopolymerization initiator.

The content of the oxime ester-based compound is preferably from 2 to 50 parts by mass, more preferably from 2 to 30 parts by mass, from the viewpoint of photocurability and developability based on 100 parts by mass of the coloring agent. When the amount is less than 2 parts by mass, the adhesion of the formed pattern to the base material is deteriorated.

<Sensitizer (H)>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxanol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-bis (diethylamino) benzophenone and the like.

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

One of these sensitizers can be used alone, or two or more of them can be used in an optional ratio as needed.
Examples of commercially available products include “KAYACURE DETX-S” (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and “CHEMARK DEABP” (4,4′-bis (diethylamino) benzophenone manufactured by Chemmark Chemical).

  More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), edited by Chusaburo Ikemori, and others. Sensitizers described in "Specially Functional Materials" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region can be contained.

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

<Thiol chain transfer agent (I)>
The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as the chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a thiol radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition has high sensitivity. .

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as a methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having four or more SH groups. By increasing the number of functional groups, the function of initiating polymerization is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

  Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropiolate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu (Tylamino) -4,6-dimercapto-s-triazine and the like, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

  These thiol-based chain transfer agents can be used alone or as a mixture of two or more.

Further, the content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0%, based on the total solid content of the coloring composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage, etc. are improved.

<Polymerization inhibitor (J)>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent exposure to light caused by diffracted light from the mask during exposure. The addition of the polymerization inhibitor has an effect of preventing the curing from progressing outside the desired pattern by the chain polymerization by exposure.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkyl catechol-based compounds such as butyl catechol and 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol Alkyl resorcinol compounds such as sinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone-based compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; trioctylphosphine oxide; triphenylphosphine oxide; Phosphine compounds such as phosphine oxide compounds, triphenyl phosphite and trisnonylphenyl phosphite , Pyrogallol, and the like phloroglucinol. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, the wrinkle of the coating film, the pattern resolution, etc. are improved.

<Ultraviolet absorber (K)>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and is a benzotriazole organic compound, a triazine organic compound, a benzophenone organic compound, a salicylate organic compound, a cyanoacrylate organic compound, and a salicylate organic compound. Organic compounds and the like can be mentioned.

  The content of the ultraviolet absorber is preferably from 5 to 70% by mass in the total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When the content of the ultraviolet absorber is smaller than the above, the effect of the ultraviolet absorber is small, and the resolution cannot be ensured, and when the content is larger than the above, the sensitivity is lowered, the pixel peeling and the hole diameter become larger than the design values. May occur.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

  Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet absorber is smaller than the above, the adhesion is weakened and the pixel peels off. When the total content is larger than the above, the sensitivity is too high and the resolution may be deteriorated.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

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

More specifically, TINUVIN P, PS, 234, 326 manufactured by BASF Corporation
Adekastab LA-29, LA-31RG, LA-32, LA-36, manufactured by ADEKA Corporation, and KEMISORB 71, 73, 74, 79 manufactured by Chemipa Kasei Corporation, 329, 384-2, 900, 928, 99-2, 1130. 279, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

  As the triazine-based organic compound, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy Reaction product of (phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester, 2,4-bis “2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- ( Hexyloxy) , 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2 -Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.

More specifically, KEMISORB 102 manufactured by Chemipro Kasei, TIN manufactured by BASF
UVIN 400, 405, 460, 477, 479, 1577ED, ADEKA ADK STAB LA-46, LA-F70, CYASSORB UV-1164 manufactured by Sun Chemical
And the like.

  As the benzophenone-based organic compound, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

More specifically, KEMIPROB 10, 11, 11S, manufactured by Chemipro Kasei Co., Ltd.
12, 111, SEPRORB 101, 107 manufactured by Cipro Kasei Co., Ltd., ADE Corporation
Adekastab 1413 manufactured by KA, UV-12 manufactured by Sun Chemical Co., Ltd., and the like.

  Examples of the salicylate organic compound include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

<Antioxidant (L)>
The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by a heat process at the time of thermosetting or ITO annealing. Can be higher. In particular, when the colorant concentration of the coloring composition is high, the amount of the crosslinking component in the coating film is small, so the use of a high-sensitivity crosslinking component or the increase in the amount of the photopolymerization initiator causes the yellowing of the heating process to become strong. Can be seen. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high transmittance of the coating film can be obtained.

  The "antioxidant" in the present invention may be any compound having a radical scavenging function or a peroxide decomposing function. Specifically, hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based antioxidants are used. And hydroxylamine-based compounds, and known antioxidants can be used. The antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of compatibility between the transmittance and the sensitivity of the coating film. Agents.

Hindered phenolic antioxidants include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2-t -Butyl-5-methylphenol), stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-) (Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 10-te Laoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3,5-tris ( 3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2′-methylenebis (6- t-butyl-4-ethylphenol), 2,2′thiodiethylbis- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3,5-diphenyl -Tert-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,6-bis (dodecylthiomethyl) -o −Crezo , Calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [3- (3-methyl-4 -Hydroxy-5-t-butylphenyl) propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4 -Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2'-thio-bis- (6-t-butyl -4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl Phenol), 2,2'-methylene - bis - (6- (1-methyl - cyclohexyl)-p-cresol), 2,4-dimethyl-6- (1-methyl - cyclohexyl) - phenol, and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

More specifically, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, K
EMINOX101, 179, 76, 9425, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, manufactured by BASF Corporation, and Cyanox CY- manufactured by Sun Chemical Co., Ltd. 1790, CY-2777 and the like.

  Hindered amine antioxidants include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetra Methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetra Methyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2 , 2,6,6-tetramethyl-4-piperidyl methacrylate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 Polycondensate with 6,6-tetramethylpiperidine, poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2 2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 4-hydroxy-2,2,6 Ester of 6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 2,6,6-pentamethyl-4-piperidyl) amino {-1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, bis (2,2,6 , 6-Tetramethyl-1- (octyloxy)- -Piperidinyl) ester, a reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-pyridyl) [[3,5-bis (1,1 dimethyl Ethyl) -4-hydroxyphenyl] methyl] butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyperidyl sebacate, poly [[6-morpholino-s-triazine-2,4-diyl ]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2,2 6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6- Hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide and the like No. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

  More specifically, ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 manufactured by ADEKA Corporation. , LA-402F, LA-502XP, KAMISTAB 29, 62, 77, 94 manufactured by Chemipura Kasei Co., Ltd., Tinuvin 249, TINUVIN 111FDL manufactured by BASF, 123, 144, 292, 5100, Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd., UV- 3529, UV-3853 and the like.

Examples of the phosphorus-based antioxidants include di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2′-methylenebis (4,6- Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4′- Isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4 ,
4-biphenyl diphosphonite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4 'isopropyl Ridendiphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) ) Pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl- -T-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl- 4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3- Bis (diphenoxyphosphonyloxy) -benzene, ethyl bisphosphite (2,4-ditert-butyl-6-methylphenyl) and the like can be mentioned. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  More specifically, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF, and Hostanox P- manufactured by Clariant Chemicals Co., Ltd. EPQ and the like.

  Examples of the sulfur-based antioxidants include 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate] and 3,3′-thio. Ditridecyl bispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o-cresol , 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

More specifically, Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd. and the like can be mentioned.

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

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

<Leveling agent (M)>
It is preferable to add a leveling agent to the photosensitive coloring composition of the present invention for the purpose of improving the coating property of the composition on a transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, and an anionic surfactant can be used.

  Examples of the silicone-based surfactant include a linear polymer comprising a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

More specifically, BYK-300, 306, 310, 313, 315 manufactured by Big Chemie
N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570, Toray Dow Corning FZ-7002, 2110 2122, 2123, 2191, 5609, X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF manufactured by Shin-Etsu Chemical Co., Ltd. -640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain or a leveling agent.

More specifically, Surflon S-242, S-243, S-420, S-611, S-651, S-386, manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-577, manufactured by DIC Corporation. , F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS -21, FC-4430, FC-4432, manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd., and 602A manufactured by Neos Corporation.

  Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrster ether, and polyoxyethylene octyl dodecyl. Ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, Bitane monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Stearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbite tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolau Rate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene Glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, alkyl imidazolines, and the like.

More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430 , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Rheodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP -O30V, Super SP-L10, AS-10V, AO-10V AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120,430V, 440V, 460V, M
S-50, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Amyt 102, 105, 105A, 302 , 320, Aminor PK-02S, L-02, Homogenol L-95, Adeka Pluronic L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, manufactured by ADEKA Corporation. 702, 704, 913R, manufactured by Kyoeisha Chemical Co., Ltd. (meth) acrylic acid-based (co) polymer Polyflow No. 75, no. 90, no. 95 and the like.

  Examples of the cationic surfactant include an alkylamine salt, an alkyl quaternary ammonium salt such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and an ethylene oxide adduct thereof.

  More specifically, there may be mentioned Acetamine 24, Coatamine 24P, 60W, 86P conc, etc., manufactured by Kao Corporation.

  Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, and monoethanolamine lauryl sulfate. And triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

  More specifically, Neogent Co., Ltd.'s Futuregent 100, 150, Adeka Co., Ltd. Adeka Hope YES-25, Adeka Coal TS-230E, PS-440E, EC-8600, etc. are mentioned.

Examples of the amphoteric surfactant include amide laurate betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl betaines such as alkyldimethylaminoacetate betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

  More specifically, examples include Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant is preferably 0.001 to 2.0% by mass based on the total solid content of the composition of the present invention, More preferably, it is 0.005 to 1.0% by mass. By being in this range, the balance between the coating properties of the coloring composition, the pattern adhesion, and the transmittance is improved.
The photosensitive coloring composition of the present invention may include only one type of surfactant, or may include two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<Storage stabilizer (N)>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. As the storage stabilizer, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, organic acids such as oxalic acid and its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

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

  Examples of the adhesion improver include vinyltrimethoxysilane, vinylsilanes such as vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth) acryl silanes such as methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyl Tyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl Mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; bis (triethoxysilylpropyl) tetrasulfide and the like Sulfide , Silane coupling agents such as isocyanates such as 3-isocyanate propyl triethoxysilane and the like. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, which is more preferable.

<Production method of coloring composition>
The coloring composition included in the present invention comprises a kneader, a two-roll mill, and a pigment in a dispersant, a binder resin and / or a solvent, preferably together with a dispersing aid (a dye derivative or a surfactant). It can be finely dispersed using various dispersing means such as a roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more kinds of pigments may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the pigment carrier may be mixed.

<Dispersion particle size of pigment>
The average dispersed particle diameter of the pigment in the coloring composition is preferably in the range of 30 to 200 nm. More preferably, it is in the range of 40 to 120 nm. Within this range, the viscosity and dispersion stability are high, and when this coloring composition is used alone or as a mixture and a photopolymerizable material is added, not only the viscosity and dispersion stability but also the sensitivity and the development speed are high. A coloring composition can be obtained, and when a color filter is produced using the same, a high quality color filter can be obtained.

As a method of measuring the dispersed particle size of the pigment, Nikkiso Co., Ltd.'s Microtrac UPA-EX150 which adopted dynamic light scattering method (FFT power spectrum method), the particle permeability was set to absorption mode, the particle shape was non-spherical, D50 may be an average diameter. As the diluting solvent for measurement, the solvent used for the dispersion is used, and it is preferable to measure the sample treated with the ultrasonic wave immediately after the sample preparation because a result with less variation can be obtained.

<Method for producing photosensitive coloring composition>
When used as a photosensitive coloring composition, it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developable or alkali-developable coloring composition includes the coloring composition, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersing aids, and additives. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Solvent>
The coloring composition of the present invention contains a solvent for facilitating formation of a colored film by coating on a substrate such as glass so as to have a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of the good coating properties of the coloring composition, the solubility of each component of the coloring composition, and the safety.

As the solvent, a solvent commonly used in the art can be used, and considering the properties such as the boiling point, the SP value, the evaporation rate, the viscosity, and the like, appropriately or separately according to the application conditions (speed, drying conditions, etc.) Used mixed.

Examples of the solvent used include ester solvents (solvents containing -COO- in the molecule and containing no -O-), ether solvents (solvents containing -O- in the molecule and containing no -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) Solvent containing no -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl -n- propyl ether, anisole, phenetole, and the like methyl anisole.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-
Ethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene Examples thereof include glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. And the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.
These solvents may be used alone or in combination of two or more.

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

<Removal of coarse particles>
The colored dispersion or the photosensitive composition of the present invention is subjected to centrifugal separation, filtration using a sintering filter or a membrane filter, or the like, to give coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm. It is preferable to remove the coarse particles and the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 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 segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

<Production method of color filter>
The color filter can be manufactured by a printing method or a photolithography method.
Since the formation of the filter segment by the printing method can be performed by repeating the printing and drying of the coloring composition prepared as the printing ink, the patterning can be performed at low cost and excellent in mass productivity as a color filter manufacturing method. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the composition be such that the ink does not dry and solidify on a printing plate or on a blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or extender.

  When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the method, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. The film dried as necessary is exposed (irradiation of radiation) through a mask having a predetermined pattern provided in contact or non-contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

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

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink-jet method or the like in addition to the above-mentioned methods, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of producing a color filter by forming each color filter segment on a transparent conductive film by electrophoresis of colloid particles using a transparent conductive film formed on a substrate. . The transfer method is a method in which a filter segment is previously formed on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

  Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. 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 is used, but is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a transparent conductive film or the like is formed as necessary.

  The color filter of the present invention is bonded to a counter substrate using a sealant, injects liquid crystal from an injection port provided in a seal portion, and then seals the injection port.If necessary, a polarizing film or a retardation film is formed on the substrate. A color liquid crystal display device is manufactured by laminating to the outside. The color liquid crystal display device includes a twisted nematic (TN), a super twisted nematic (STN), an in-plane switching (IPS), a vertical alignment (VA), an optically-convened bend (OCB). ) Can be used in a liquid crystal display mode for performing colorization using a color filter.

  Further, the color filter of the present invention can be used for manufacturing a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like, in addition to the color liquid crystal display device.

<Liquid crystal display device>
A liquid crystal display device including the color filter of the present invention will be described.
A liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. However, in the present invention, it is preferable to use a white LED from the viewpoint that the red reproduction region is widened. FIG. 1 is a schematic sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged so as to face each other, and a liquid crystal LC is sealed between them.

The liquid crystal LC is aligned according to a drive mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), and the like. On the inner surface of the first transparent substrate 11,
A TFT (thin film transistor) array 12 is formed, on which a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is further formed thereon. Is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

Examples of the white LED light source include a light source in which a fluorescent filter is formed on the surface of a blue LED, and a light source in which a phosphor is contained in a resin package of a blue LED, and a wavelength at which the emission intensity is maximized within a range of 430 nm to 485 nm ( λ3), has a wavelength (λ4) at which the emission intensity is maximum in the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at λ3 to the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 to the emission intensity I5 at the wavelength λ5 (I5 / I3 ) Having a spectral characteristic of 0.1 or more and 1.3 or less and a wavelength (λ1) at which the emission intensity becomes maximum within a range of 430 nm to 485 nm. And has a second emission intensity peak wavelength (λ2) in the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 to 0. A white LED light source (LED2) having a spectral characteristic of 0.7 or less is preferable.

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia), NSSW304D (manufactured by Nichia), and the like.

  Hereinafter, the present invention will be described with reference to examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

  Prior to the examples, each measuring method will be described.

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

(Dispersion particle size measurement)
Using Nikkiso Co., Ltd. Microtrac UPA-EX150, which adopted dynamic light scattering method (FFT power spectrum method), the particle permeability was set to absorption mode, the particle shape was made non-spherical, and D50 was made the average diameter. The solvent used for the dispersion was used as the diluting solvent for measurement, and the measurement was performed on the sample treated with ultrasonic waves immediately after the sample preparation.

Also, the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g)
) Is as follows.

(Average molecular weight of resin)
The number average molecular weight (Mn) and the mass average molecular weight (Mw) of the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as an apparatus, two separation columns were connected in series, and both fillers were connected using "TSK-GEL SUPER HZM-N" in a double column. The measurement was performed at a flow rate of 0.35 ml / min using a THF solution as an eluent at 0 ° C.
The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliter was injected. All molecular weights are in terms of polystyrene.

<Acid value of resin (mgKOH / g)>
To 0.5 to 1 g of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant, and an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) ), And the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Ammonia salt value of resin having cationic group in side chain>
The ammonium salt value of a resin having a cationic group in a side chain is a value obtained by titrating with a 5% aqueous solution of potassium chromate with a 0.1N aqueous solution of silver nitrate using an aqueous solution of potassium chromate as an indicator, and converting it to an equivalent of potassium hydroxide. , And the ammonium salt value of the nonvolatile content.

<Production method of micronized pigment>
<Method for producing diketopyrrolopyrrole pigment>
(Diketopyrrolopyrrole pigment 1)
Under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated by molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube, and the mixture was heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 4-bromobenzonitrile 1
53.6 parts were added and dissolved by heating to 90 ° C. while stirring to prepare a solution of these mixtures. A heated solution of this mixture was slowly dropped into the above-described alcoholate solution heated to 100 ° C. at a constant rate over 2 hours while stirring vigorously. After completion of 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. Further, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a glass-made reaction vessel equipped with a jacket, and cooled to -10 ° C. The cooled mixture was cooled to 75 ° C. while rotating a shear disk having a diameter of 8 cm at 4,000 rpm using a high-speed stirring disperser, and the alkali metal salt of the diketopyrrolopyrrole compound obtained earlier was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole-based compound at 75 ° C while cooling so that the temperature of the mixture of methanol, acetic acid, and water always keeps a temperature of -5 ° C or less. , And was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals precipitated, and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C., and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to form a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing with crystal transition and washing. Subsequently, the resulting aqueous paste of the diketopyrrolopyrrole-based compound was separated by filtration with an ultrafiltration machine, dried at 80 ° C. for 24 hours, and crushed to obtain 150.8 parts of the diketopyrrolopyrrole pigment 1 by pulverization. Obtained.

(Diketopyrrolopyrrole pigment 2)
While putting 220 parts of tert-amyl alcohol in the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of a compound of the following formula (20) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in the reaction vessel 2. This was dissolved, and this was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., and 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol to obtain 88.1 parts of diketopyrrolopyrrole pigment 2. .

Equation (20)

(Diketopyrrolopyrrole pigment 3)
Except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile, the same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out, and 83.9 parts of diketopyrrolopyrrole pigment 3 was obtained. Obtained.

(Diketopyrrolopyrrole pigment 4)
Diketopyrrolopyrrole pigment 4 was converted to 87.0 parts in the same manner as in the preparation of diketopyrrolopyrrole pigment 2, except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide. I got a copy.

(Diketopyrrolopyrrole pigment 5)
Except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide, the same procedure as in the preparation of diketopyrrolopyrrole pigment 2 was carried out. I got a copy.

(Diketopyrrolopyrrole pigment 6)
Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, the same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out to obtain the diketopyrrolopyrrole pigment 6 of 87. 1 part was obtained.

(Diketopyrrolopyrrole pigment 7)
While putting 220 parts of tert-amyl alcohol in the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (21) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in the reaction vessel 2. This was dissolved, and this was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., and 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol to obtain 87.8 parts of diketopyrrolopyrrole pigment 7. .

Equation (21)

<Preparation of fine pigment>
(Production of micronized pigment (A-1))
100 parts of diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride and 120 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture is poured into warm water, and stirred for 1 hour while being heated to about 80 ° C. to form a slurry. After filtration and washing to remove salt and diethylene glycol, the mixture is dried at 80 ° C. for 24 hours, and ground. As a result, 96.9 parts of a finely divided pigment (A-1) having a diketopyrrolopyrrole-based pigment was obtained.

(Production of micronized pigment (A-2))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 2, the same procedure as in the production of the finely divided pigment (A-1) was carried out. A-2) 96.5 parts were obtained.

(Production of micronized pigment (A-3))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 3, the production was performed in the same manner as in the production of the finely divided pigment (A-1). A-3) 98.1 parts were obtained.

(Production of micronized pigment (A-4))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 4, it was carried out in the same manner as in the production of the finely divided pigment (A-1). A-4) 98.0 parts were obtained.

(Production of micronized pigment (A-5))
Except that 100 parts of the diketopyrrolopyrrole pigment 5 was changed to 100 parts of the diketopyrrolopyrrole pigment 5, the production was performed in the same manner as in the production of the finely divided pigment (A-1). A-5) 98.4 parts were obtained.

(Production of micronized pigment (A-6))
Except that 100 parts of the diketopyrrolopyrrole pigment 6 was changed to 100 parts of the diketopyrrolopyrrole pigment 6, the production was performed in the same manner as in the production of the finely divided pigment (A-1). A-6) 97.5 parts were obtained.

(Production of micronized pigment (A-7))
Except that 100 parts of the diketopyrrolopyrrole pigment 1 was changed to 100 parts of the diketopyrrolopyrrole pigment 7, it was carried out in the same manner as in the production of the finely divided pigment (A-1). A-7) 97.5 parts were obtained.

(Production of micronized pigment (A-8))
Diketopyrrolopyrrole pigment 1 was obtained from commercially available C.I. I. Pigment Red 254 ("Irgafor Red B-CF" manufactured by Ciba Specialty Chemicals) was carried out in the same manner as in the production of the finely divided pigment (A-1), and a diketopyrrolopyrrole-based finely divided pigment (A- 8) 97.3 parts were obtained.

(Fine pigments A-9 to 13)
In accordance with the examples of JP-A-2017-111398, finely divided aluminum phthalocyanine pigments represented by the following formulas 51 to 55 (A-9 to 13) were prepared. The structure is shown below.

(Fine pigment A-9)
Equation (51)

(Micronized pigment A-10)
Equation (52)

(Micronized pigment A-11)
Equation (53)

(Micronized pigment A-12)
Equation (54)

(Fine pigment A-13)
Equation (55)

(Fine pigment (A-14))
Phthalocyanine green pigment C.I. I. Pigment Green 58 ("FASTGEN GREENA110" manufactured by DIC), 100 parts of sodium chloride and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C for 6 hours. The kneaded material was poured into 3,000 parts of warm water, stirred for 1 hour while heating to 70 ° C to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol. 97 parts of the modified pigment (A-14) were obtained.

(Fine pigments (A-15 to 17))
According to the examples of JP-A-2012-226110, finely divided quinophthalone pigments (A-15 to 17) represented by the following formulas (56) to (58) were prepared. The structure is shown below.

(Micronized pigment A-15)
Equation (56)

(Fine pigment A-16)
Equation (57)

(Micronized pigment A-17)
Equation (58)

(Fine pigment (A-18))
C. I. Pigment Yellow 138 (PY138) ("PARIOTOR YELLOW K0960-HD" manufactured by BASF), 100 parts of sodium chloride, and 180 parts of diethylene glycol are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and are heated at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2,000 parts of warm water, stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove the salt and the solvent, dried at 80 ° C. all day and night, and dried in 95 parts of fine powder. A pigment (A-18) was obtained.

Table 1 shows the average primary particle size (nm) of each fine pigment.

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

(Dye 01 (AR52-JK))
C. In the following procedure. I. Dye 01 (AR52-JK), which is a salt-forming compound comprising Acid Red 52 and Resin 1 having a cationic group in a side chain, was produced.
To 2000 parts of water, 30 parts of a resin 1 having a cationic group in a side chain in terms of a nonvolatile content were added, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and added dropwise to the resin solution. After the dropwise addition, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was determined that a salt-forming compound was obtained, with the end point at which bleeding disappeared as the end point. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing the water content with a drier, and dried with 32 parts of C.I. I. Dye 01 (AR52) which is a salt forming compound of Acid Red 52 and Resin 1 having a cationic group in a side chain.
-JK). At this time, C.I. in Dye 01 (AR52-JK) was used. I. The content of the effective dye component derived from Acid Red 52 was 25% by mass.

<Method for producing dye solution>
(Dye solution (DS-01))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 5.0 μm to prepare a dye solution (DS-01).
Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

<Dye derivative>
The following dye derivatives were used.
Dye derivative (1)

Dye derivative (2)

Dye derivative (3)

Dye derivative (4)

Dye derivative (5)

(Production of Resin Dispersant (C1))
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), 0.2 parts of monobutyltin oxide as a catalyst Was charged and replaced with nitrogen gas, and reacted at 120 ° C. for 5 hours (first step). The measurement of the acid value confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of solid content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate , 50 parts of methacrylic acid, and 663 parts of PGMAc, and the reaction vessel was heated to 80 ° C, 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). The solid content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 500 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and the IR was 2270 cm based on the isocyanate group. The reaction was continued until the disappearance of the -1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (C1) solution having a solid content of 30%. The resulting dispersant had an acid value of 68, an equivalent weight of unsaturated double bond of 1593, and a weight average molecular weight of 13,000.

(Production of resin type dispersant (C2))
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. Then, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 73.3 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours. Measurement of the acid value confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (C2) solution having a solid content of 30%. The resulting dispersant was a white solid at room temperature, and had an acid value of 49 mgKOH / g.

(Production of Resin Dispersant (C3))
A separable four-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, charged with 1500 parts of cyclohexanone, heated to 80 ° C. and replaced with nitrogen in the reaction vessel. 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M-110” manufactured by Toagosei Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate, A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin-type dispersant (C3) solution having a solid content of 30% and a weight average molecular weight of 24,000.

(Production of resin type dispersant (C4-1) and vinyl resin (C4-2)) 80 parts of methyl methacrylate, 120 parts of ethyl acrylate in a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer. And 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 4.4 parts of 3-mercapto-1,2-propanediol, 0.2 parts of 2,2′-azobisisobutyronitrile was divided into 20 portions. The reaction was continued at 80 ° C. for 12 hours, and the solid content measurement confirmed that 95% had reacted. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was added at 120 ° C. for 2 hours. The reaction was performed at 80 ° C. for 5 hours. It was confirmed by titration that 90% or more of the acid anhydride was half-esterified, and a resin-type dispersant (C4-1) having an acid value of 44 mgKOH / g per solid content was obtained. Further, the solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (C4-1) solution having a solid content of 30%. 133 parts of methoxypropyl acetate was charged into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 100 ° C. while purging with nitrogen. 200 parts of N, N-dimethylaminoethyl methacrylate, 61 parts of methoxypropyl acetate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged into a dropping tank, and the mixture was stirred until it became uniform. The mixture was dropped into the tank over 2 hours, and the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin (C4-2) having a tertiary amino group having an amine value per solid of 345 mgKOH / g and a number average molecular weight of 2,500 (Mn) was obtained. The solid content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersant (C4-2) solution having a solid content of 30%.

<Production example of binder resin (D)>
(Preparation of binder resin (D-1) solution)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From a tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 , A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the non-volatile content was measured. The propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the non-volatile content was 20%. Acetate was added to prepare a binder resin (D-1) solution. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (D-2) liquid)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer in a separable four-necked flask, heated to 80 ° C., and purged with nitrogen after the inside of the reaction vessel was replaced with nitrogen. From a tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, nitrogen gas was stopped with respect to the total amount of the obtained copolymer solution, and the mixture was stirred while injecting dry air for 1 hour. After cooling to room temperature, 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK) A mixture of 6.5 parts (MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20%. Thus, a binder resin (D-2) was prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin (D-3) liquid)
370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirrer, the temperature was raised to 80 ° C, and the flask was purged with nitrogen. 18 parts of millphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Parts of the mixture were added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 part of triethylamine were successively added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acetate was added to prepare a binder resin (D-3) solution. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin (D-4) liquid)
A separable flask equipped with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, A mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) and 40 parts of propylene glycol monomethyl ether acetate was stirred and mixed well. A mixture was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate.
The reaction vessel was charged with 395 parts of propylene glycol monomethyl ether acetate and, after purging with nitrogen, heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction tank was stabilized at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over a period of 135 minutes while maintaining the temperature at 90 ° C.
After 60 minutes from the completion of the dropwise addition, the temperature was raised to 110 ° C. in the reaction vessel. After maintaining at 110 ° C. for 3 hours, a gas introducing tube was attached to the separable flask, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (volume ratio) was started. Next, glycidyl methacrylate 7 was added to the reaction vessel.
0 parts, 0.4 parts of 2,2′-methylenebis (4-methyl-6-t-butylphenol),
0.8 part of triethylamine was charged and reacted at 110 ° C. for 12 hours. Thereafter, 150 parts of propylene glycol monomethyl ether acetate was added, and the mixture was cooled to room temperature. About 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Propylene glycol monomethyl ether acetate was added so as to be 20% by weight to obtain a binder resin (D-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per solid was 2 mgKOH / g.

<Method for producing colored composition (single color)>
[Example 1]
(Preparation of coloring composition (R-1))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered with a 0 μm filter to prepare a coloring composition (R-1) having a nonvolatile component content of 24.3% by mass.
Pigment (A-1): 20.0 parts Dye derivative (1): 0.5 parts Resin-type dispersant ((C1): 30% non-volatile content liquid): 2.0 parts Binder resin (D-1: non-volatile content) 20% liquid): 16.0 parts Solvent (P): 61.5 parts

[Examples 2 to 56, Comparative Examples 1 to 3] (Preparation of coloring composition (R-2 to 59))
Coloring compositions (R-2 to 59) were prepared in the same manner as in Example 1, except that the material type and weight were changed as shown in Table 2. Table 2 shows the respective dispersed particle diameters.

<Method for producing colored composition (colorant mixture)>
[Example 101]
(Preparation of coloring composition (X-1))
The following ingredients were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to give a colored composition (X-1)
I got
Pigment dispersion (R-1: 24.3% non-volatile content): 40 parts Pigment dispersion (R-15: 24.3% non-volatile content): 16 parts Binder resin (D-1: 20% non-volatile content) ): 32 parts Solvent (P): 12 parts

[Examples 102 to 124, Comparative Examples 101 to 103] (Preparation of Colored Compositions (X-2 to 27))
Coloring compositions (X-2 to 27) were prepared in the same manner as in Example 101, except that the material type and mass were changed as described in Table 3.

<Evaluation of coloring composition>
About the obtained coloring composition (R-1 to 59, X-1 to 27), the test regarding viscosity and storage stability was performed by the following method. Table 4 shows the test results.

<Measurement of viscosity characteristics>
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer ("ELD viscometer" manufactured by Toki Sangyo Co., Ltd.). The ranking of the evaluation is as follows.
：: viscosity 4.0 or more and less than 20.0: good level ×: viscosity 20 or more: level unsuitable for practical use

(Storage stability)
The coloring compositions obtained in Examples and Comparative Examples were evaluated for storage stability by the following method.
The initial viscosity on the day following the preparation of the coloring composition and the temporal viscosity accelerated for one week at 40 ° C. were measured at 25 ° C. using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). The measurement was performed under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change of viscosity over time was calculated by the following formula, and the storage stability was evaluated in two steps.
[Rate of change in viscosity over time] = | ([initial viscosity]-[viscosity over time]) / [initial viscosity] | × 100
: Change rate of less than 10% ×: Change rate of 10% or more

<Method for producing photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to form a photosensitive coloring composition (Y
-1) was obtained.
Coloring composition (X-1: nonvolatile content 20%): 50.0 parts Binder resin (D-2: nonvolatile content 20%): 15.0 parts Thermosetting compound (E-1): 1.0 part Heat Curable compound (E-2): 1.0 part Photopolymerizable monomer (F): 3.0 parts Photopolymerization initiator (G): 1.8 parts Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 parts UV absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M : Nonvolatile content: 3%): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 part Solvent (P): 26.0 parts

[Examples 202 to 282, Comparative Examples 201 to 206] (Preparation of photosensitive coloring composition (Y-2 to 88))
Photosensitive coloring compositions (Y-2 to 88) were produced in the same manner as in Example 201, except that the types of the coloring composition and the binder resin solution of Example 201 were changed as described in Table 5.
In addition, about each raw material, it is as follows.

<Thermosetting compound (E)>
・ Epoxy compound (E-1)
(E-1-1) 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2′-bis (hydroxymethyl) -1-butanol
[TTA-3150 (Kusumoto Kasei Co., Ltd.)],
(E-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were mixed in equal amounts to obtain an epoxy compound (E-1).
-Oxetane compound (E-2):
3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Alon Oxetane OXT-221 (Toagosei Co., Ltd.)]

<Polymerizable compound (F)>
(F-1) Trimethylolpropane triacrylate
[Aronix M309 (Toagosei Co., Ltd.)]
(F-2) dipentaerythritol penta and hexaacrylate (E-2)
[Aronix M402 (Toagosei Co., Ltd.)]
(F-3) Polybasic acidic acrylic oligomer
[Aronix M520 (Toagosei Co., Ltd.)]
(F-4) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (Nippon Kayaku)]

(F-5) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a five-neck reaction vessel having a capacity of 1 liter of polyfunctional urethane acrylate as described below, and reacted at 60 ° C. for 8 hours to obtain a (meth) acryloyl group A product containing a polyfunctional urethane acrylate (F-5) having the following formula: The proportion of the polyfunctional urethane acrylate (F-5) in the product was 70% by mass, and the remainder was other photopolymerizable It was occupied by monomers, and it was confirmed by IR analysis that there was no isocyanate group in the reaction product.

(F-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(F-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
As described above, (F-1) to (F-7) were mixed in the same amounts, respectively, to obtain a photopolymerizable monomer (E).

<Photopolymerization initiator (G)>
(G-1) 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]
(G-2) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(G-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Lucirin TPO (made by Ciba Japan)]
(G-4) 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole
[Bimidazole (Kurokin Kasei)]
(G-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(G-6) ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H
-Carbazol-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (BASF Japan)]
(G-7) 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Irgacure 2959 (manufactured by BASF Japan)]
(G-8) bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
As described above, (G-1) to (G-8) were mixed in the same amounts, respectively, to obtain a photopolymerization initiator (G).

<Sensitizer (H)>
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (Nippon Kayaku)]
(H-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemmark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amounts, respectively, to obtain a sensitizer (H).

<Thiol chain transfer agent (I)>
(I-1) Trimethylolethanetris (3-mercaptobutyrate)
[TEMB (Showa Denko)]
(I-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (Showa Denko)]
(I-3) pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (Sakai Chemical Industry)]
(I-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (I-1) to (I-5) were mixed in the same amounts, respectively, to obtain a thiol chain transfer agent (I).

<Polymerization inhibitor (J)>
(J-1) 3-methylcatechol (J-2) methylhydroquinone (J-3) tert-butylhydroquinone or more, and mixing (J-1) to (J-3) in the same amounts, respectively, (J).

<Ultraviolet absorber (K)>
(K-1) 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (K-1) and (K-2) were mixed in the same amounts, respectively, to obtain an ultraviolet absorber (K).

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

<Leveling agent (M)>
1 copy of "BYK-330" manufactured by Big Chemie
1 copy of MegaFac F-551 manufactured by DIC Corporation
A mixed solution in which 1 part of "Emulgen 103" manufactured by Kao Corporation is dissolved in 97 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer (N)>
(N-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine ("TPP" manufactured by Hokuko Chemical Co., Ltd.)
As described above, (N-1) and (N-2) were mixed in the same amounts, respectively, to obtain a storage stabilizer (N).

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

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

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. Table 6 shows the results of the test.

<Sensitivity evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.2 μm, and prebaked at 120 ° C. for 120 seconds. Next, after cooling the substrate to room temperature, the substrate was exposed to ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Thereafter, the substrate was spray-developed with a 23 ° C. aqueous sodium carbonate solution, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 230 ° C. for 30 minutes to form a stripe on the substrate. Colored pixels were formed.
The sensitivity of the colored composition was evaluated based on the minimum irradiation exposure amount at which the pattern of the formed colored pixels was completed according to the image size of the photomask. The ranking of the evaluation is as follows.
○: less than 100mJ / cm ² △: 100 or more, 150mJ / cm ² less than ×: 150mJ / cm ² or more

<Developing speed evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater to a dry film thickness of 1.0 μm, and dried at 70 ° C. for 20 minutes.
2 ml of a 2% by weight aqueous solution of potassium hydroxide was dropped on the coating film, and the time until the coating thickness was not dissolved was measured to evaluate the developing speed of the coloring composition. The ranking of the evaluation is as follows.
：: less than 10 seconds △: 10 seconds or more, less than 15 seconds ×: 15 seconds or more

<Measurement of viscosity characteristics>
The viscosity at a rotation speed of 20 rpm was measured using an E-type viscometer ("ELD viscometer" manufactured by Toki Sangyo Co., Ltd.).
The ranking of the evaluation is as follows.
〇: Viscosity 2.0 or more and less than 10.0: Good level X: Viscosity 10.0 or more: Level not suitable for practical use

(Storage stability)
The storage stability of the photosensitive coloring compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity of the next day after the preparation of the photosensitive coloring composition and the time-dependent viscosity accelerated for one week at 40 ° C. were measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). The temperature was measured at 50 ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change of viscosity over time was calculated by the following formula, and the storage stability was evaluated in two steps.
[Rate of change in viscosity over time] = | ([initial viscosity]-[viscosity over time]) / [initial viscosity] | × 100
: Change rate of less than 10% ×: Change rate of 10% or more

Reference Signs List 10 liquid crystal display device 11 transparent substrate 12 TFT array 13 transparent electrode layer 14 alignment layer 15 polarizing plate 21 transparent substrate 22 color filter 23 transparent electrode layer 24 alignment layer 25 polarizing plate 30 backlight unit 31 white LED light source LC liquid crystal

Claims (5)

A colored composition comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and a binder resin (D), wherein the pigment (A) is an aluminum phthalocyanine pigment, a zinc phthalocyanine pigment, a halogen At least one selected from the group consisting of diketopyrrolopyrrole pigments and quinophthalone pigments, the average primary particle diameter of which is 10 to 80 nm, and the resin-type dispersant (C) has the following (C1) to (C4) A coloring composition comprising the acidic resin-type dispersant represented by any one of (C4), and wherein the coloring composition has an average dispersed particle size of 30 to 200 nm.
(C1): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound. Part A, a vinyl polymer obtained by radical polymerization of one or more ethylenically unsaturated monomers selected from the group consisting of an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group A dispersant comprising a part B, wherein the vinyl polymer part B has a (meth) acryloyl group.
(C2): a dispersant represented by the following general formula (1).
Formula _{(1) (HOOC-) m -R} 1 - (- COO - [- R 3 -COO-] n -R 2) t
Wherein R ¹ is a tetravalent tetracarboxylic acid compound residue, R ² is a monoalcohol residue, R ³ is a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4 -M).)
(C3): a dispersant containing, as a copolymerization component, an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group, and another ethylenically unsaturated monomer.
(C4): Polyester having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a hydroxyl group in a hydroxyl group-containing compound A dispersant comprising a part A and a vinyl polymer part B obtained by radical polymerization of one or more ethylenically unsaturated monomers. 2. The colored composition according to claim 1, further comprising a dye. A photosensitive coloring composition comprising the coloring composition according to claim 1, a polymerizable compound (F), and a photopolymerization initiator (G). A color filter formed using the photosensitive coloring composition according to claim 3.   A liquid crystal display device comprising the color filter according to claim 4.