JP7263759B2 - Coloring composition, photosensitive coloring composition, color filter, color liquid crystal display device - Google Patents

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, and a coloring composition used in the manufacture of a color filter used in electronic paper and the like, and a photosensitive coloring composition, Also, the present invention relates to a color filter and a color liquid crystal display device having filter segments formed by using the same.

The color filter is formed by arranging two or more fine band-shaped filter segments with different hues in parallel (stripe) or crossing each other on a transparent substrate such as a glass substrate, or are arranged so as to be arranged in order in each of the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundred microns, and are orderly arranged in a predetermined array for each hue.
At present, the mainstream method for manufacturing color filters is a method called a pigment dispersion method, in which pigments having various resistances such as light resistance and heat resistance are used as coloring agents. In addition, 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 with a pattern corresponding to filter segments of a certain color. Next, the unexposed portion of the coating film is removed by development, and then, if necessary, treatment such as heating is performed. As a result, a filter segment pattern for the first color is obtained. By performing the same operation, filter segment patterns of other colors are formed to complete the color filter.

In recent years, high color reproducibility of displays has become an important trend. In order to improve the color reproducibility of displays, studies have focused on improving the color reproducibility of backlights, but it is also necessary to use very dark colors for color filters in order to improve the color reproducibility. In such a case, in the exposure process for forming the color filter pattern, the amount of light reaching the bottom of the coating film becomes weak, so photocuring tends to be insufficient, resulting in the problem of not being able to obtain a pattern of the desired shape. do.

Specifically, the dimension of the pattern obtained in the color filter manufacturing process is required to have dimensional stability within a certain extent when the exposure dose in the exposure process is varied. Such dimensional stability tends to deteriorate in photosensitive coloring compositions that achieve high color reproducibility. Similarly, a photosensitive coloring composition that achieves high color reproduction tends to deteriorate the linearity of the pattern.

Various methods have been examined 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, pattern shape and dimensional stability are realized by providing an anchor layer on a substrate. In Patent Document 3, a polymer having a specific structure is added to a photosensitive composition to realize stability of pattern dimensions at a low exposure dose. 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, the high dimensional stability and linearity required for color filters today have not been sufficiently achieved, and further improvements are required.

JP 2013-254047 A JP 2013-073115 A JP 2012-108227 A JP 2011-002796 A JP 2010-039475 A

The present invention provides a coloring composition having excellent viscosity stability, a photosensitive coloring composition having high sensitivity, a high development speed, and excellent viscosity stability, and a color filter formed using the photosensitive coloring composition. , an object of the present invention is to provide 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, a zinc phthalocyanine It is at least one selected from the group consisting of pigments, halogenated diketopyrrolopyrrole pigments, and quinophthalone pigments, and has an average primary particle size of 10 to 80 nm, and the resin-type dispersant (C) contains the following A coloring composition comprising an acidic resin-type dispersant represented by any one of (C1) to (C4), wherein the coloring composition has an average dispersed particle size of 30 to 200 nm.
(C1): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A vinyl polymer obtained by radical polymerization of part A and at least one ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having no hydroxyl group and ethylenically unsaturated monomers having a hydroxyl group. A dispersant comprising part B, wherein the vinyl polymer part B has a (meth)acryloyl group.
(C2): A dispersant represented by the following general formula (1).
General formula (1) (HOOC-) _m - ^R1 -(-COO-[- ^R3 -COO-] _n - ^R2 ) _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, t is (4 -m).)
(C3): A dispersant containing an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group and another ethylenically unsaturated monomer as copolymer components.
(C4): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A dispersant comprising part A and a vinyl polymer part B obtained by radically polymerizing one or more ethylenically unsaturated monomers.

[2] The coloring composition of [1], further comprising a dye.

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

A color filter formed using the photosensitive coloring composition described in [3].

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

The present invention provides a high-quality color filter and a color liquid crystal display device because it is a coloring composition having excellent viscosity stability, a photosensitive coloring composition having high sensitivity, a high development speed, and excellent viscosity stability. can.

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

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

The present invention is a coloring 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, zinc 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) is the following (C1) It is characterized by containing an acidic resin-type dispersant represented by any one of (C4) and having an average dispersed particle size of 30 to 200 nm.
(C1): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A vinyl polymer obtained by radical polymerization of part A and at least one ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having no hydroxyl group and ethylenically unsaturated monomers having a hydroxyl group. A dispersant comprising part B, wherein the vinyl polymer part B has a (meth)acryloyl group.
(C2): A dispersant represented by the following general formula (1).
General formula (1) (HOOC-) _m - ^R1 -(-COO-[- ^R3 -COO-] _n - ^R2 ) _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, t is (4 -m).)
(C3): A dispersant containing an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group and another ethylenically unsaturated monomer as copolymer components.
(C4): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A dispersant comprising part A and a vinyl polymer part B obtained by radically polymerizing one or more ethylenically unsaturated monomers.

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

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

(other pigments)
As the pigment, organic or inorganic pigments can be used singly or in combination of two or more. As the pigment, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by color index numbers.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291 and the like. In addition, diketopyrrolopyrrole pigments described in JP-A-2011-523433 and JP-A-2017-138417, or azo pigments described in JP-A-2014-112527, azo described in JP-A-2013-161026 A pigment etc. are mentioned. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, more preferably C.I. I. Pigment Red 177, 254, 291.

Further, in the red colored composition, C.I. I. An orange pigment such as 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 blue pigments 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 viewpoint 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, more preferably C.I. I. Pigment Blue 15:6. Moreover, you may use the below-mentioned purple pigment together with a blue coloring composition.

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

Examples of green pigments 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 2012-155231 A, JP 2
Pigments described in 016-153481 can be mentioned, but are not particularly limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62 or 63.
Further, the green coloring composition may be used in combination with a yellow pigment described later.

Yellow pigments include, 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, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, and pigments described in JP-A-2012-226110. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

Cyan-colored compositions for forming cyan-colored filter segments include, for example, C.I. I. Blue pigments such as Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16 and 81 can be used singly 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. Purple pigments and red pigments such as Pigment Red 144, 146, 177, 169, 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 oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, and amber. , synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

<Other coloring agents>
The photosensitive composition of the present invention can contain coloring agents such as dyes other than the pigment (A).
<Dye (a)>
Any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, and the like can be used as dyes. Moreover, it may be in the form of a derivative of these or a lake pigment obtained by turning a dye into a lake.

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

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

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

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). 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, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

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

<Refinement of pigment>
The method for refining the pigment used in the photosensitive coloring composition of the present invention is not particularly limited. It can be made finer by salt milling treatment or the like by a kneader method, which is a type of grinding. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 10 to 80 nm. If it is smaller than 10 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 80 nm, it may not be possible to obtain a sufficient contrast ratio. For these reasons, the average primary particle size is more preferably in the range of 15 to 70 nm.

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

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

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, most preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

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

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

As the dye derivative used in the present invention, known dye derivatives 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 carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, a phenyl group, and phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group. Since the resin-type 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.
Examples of organic dyes include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, benzo Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo. be done.

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine As the dye derivative, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, as the anthraquinone dye derivative, JP-A-63-26467
4, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, particularly JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, JP-A-2011-162662 as a thiazineindigo-based dye derivative, 2007-314785, as triazine dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004- 217842, JP 2007-314681, JP 2009-57478 as a benzoisoindole dye derivative, JP 2003-167112 as a quinophthalone dye derivative, JP 2006-291194 Publications, JP-A-2008-31281, JP-A-2012-226110, as a naphthol dye derivative, JP-A-2012-208329, JP-A-2014-5439, as an azo dye derivative, JP-A 2001-172520, JP 2012-172092, as an acidic substituent, JP 2004-307854, as a basic substituent, JP 2002-201377, JP 2003-171594 , JP-A-2005-181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a sexual group is synonymous with a dye derivative.

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

[Diketopyrrolopyrrole Dye Derivative]

一般式（１０３）
[Phthalocyanine dye derivative]

general formula (103)

[Anthraquinone dye derivative]

一般式（１０８）
[Quinacridone dye derivative]

general formula (108)

[Dioxazine dye derivative]

一般式（１１１）
[Thiazine indigo dye derivative]

general formula (111)

一般式（１１２）
[Triazine dye derivative]

general formula (112)

一般式（１１３）
[Benzisoindole dye derivative]

general formula (113)

[Quinophthalone dye derivative]

一般式（１２９）
[Naphthol dye derivative]

general formula (129)

[Azo dye derivative]

一般式（１３３）

general formula (133)

In 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 are each independently hydrogen Atom, hydroxyl group, optionally substituted alkyl group, optionally substituted alkoxy group, optionally substituted phthalimidoalkyl group, optionally substituted acyl group, amino group, sulfo group, carboxyl group, phosphoric acid group, halogen group, and groups represented by 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, at least one is a substituent other than a hydrogen atom. Moreover, when there is only one substituent in one molecule, it is a substituent other than a hydrogen atom.

In general formula (113), R ₁₁₈ is a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, alkoxy group, aryloxy group, —SO ₂ R ₁₇₇ or —NR ₁₇₈ R ₁₇₉ . provided that R ₁₇₇ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, or a halogen atom, and R ₁₇₈ and R ₁₇₉ are each independently a hydrogen atom , an alkyl group having 1 to 12 carbon atoms, or R ₁₇₈ and R ₁₇₉ together represent a heterocyclic ring which may contain an additional nitrogen, oxygen or sulfur atom.
R ₁₁₉ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted acyl group.
R ₁₂₀ , R ₁₂₁ , R ₁₂₃ to R ₁₂₈ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, a halogen atom, a cyano group, a substituent or NR ₁₈₀ R ₁₈₁ . provided that R ₁₈₀ and R ₁₈₁ are each independently a hydrogen atom, an optionally substituted alkyl group, or R ₁₈₀ and R ₁₈₁ together may contain a further nitrogen, oxygen or sulfur atom represents a good heterocycle.
R ₁₂₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted acyl group, or a group represented by general formulas (150) to (155).

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

In the general formulas (150) to (155),
X ₁ represents a direct bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC ₆ H ₄ CO-, or -CONHC ₆ H ₄ -.
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 optionally substituted arylene group, or an optionally substituted heteroaromatic ring, and these groups are —NR ₁₇₀ —, —O—, —SO ₂ They may be mutually linked by a divalent linking group selected from - or CO-.
Y ₃ represents a direct bond, -NR ₁₇₀ - or -O-.
o represents an integer from 0 to 20;
_M1 represents a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom or an iron atom.
_M2 represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _M2 .
R ₁₅₀ and R ₁₅₁ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₅₀ and R ₁₅₁ represents an optionally substituted heterocyclic ring which together contains an additional nitrogen, oxygen or sulfur atom.
R ₁₅₂ to R ₁₅₆ and R ₁₅₉ to R ₁₆₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted 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 ,
—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 optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R ₁₇₂ to R ₁₇₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or a represents an alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

一般式（１５６）

general formula (156)

In the general formula (156), Z ₁ represents -NR ₁₇₀ -, -CONH- or -O-, and Z ₂ is an optionally substituted alkylene group or an optionally substituted alkenylene group. , represents an arylene group which may have a substituent, and these groups are mutually bonded by a divalent linking group selected from —NR ₁₇₀ —, —O—, —SO ₂ — or CO— good too. However, R ₁₇₀ has the same definition as R ₁₇₀ in general formulas (150) to (155).
R ₁₅₀ and R ₁₅₁ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₅₀ and R ₁₅₁ together represents an optionally substituted heterocyclic ring containing a further nitrogen, oxygen or sulfur atom.

一般式（１５７）

general formula (157)

_In general formula (157) _, Z ₃ is _a single _{bond connecting} the _triazine ring and the nitrogen atom _;
—Z ₄ —SO ₂ —, —NR ₁₇₅ —Z ₄ —SO ₂ NR ₁₇₆ —, —O—Z ₄ —CO—,
—OZ ₄ —CONR ₁₇₅ —, —OZ ₄ —SO ₂ —, or OZ ₄ —SO ₂ NR ₁₇₅ —, wherein 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, Z ₄ is an alkylene group which may have a substituent, a substituent represents an alkenylene group which may have a or an arylene group which may have a substituent.
R ₁₅₂ to R ₁₅₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or polyoxyalkylene represents a group.

一般式（１５８）

general formula (158)

一般式（１５９）

general formula (159)

In general formula (159), X ₂ represents -SO ₂ -, -CO-, -NH-, -SO ₂ NH-, -NHSO ₂ -, -CONH- or -NHCO-, and R ₁₆₃ to R ₁₆₇ each independently represents a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, or a group represented by general formulas (150) to (155).

The alkyl group which may have a substituent is preferably a linear alkyl group having 1 to 20 carbon atoms as the alkyl group, and the substituent which may have is preferably hydrogen or a halogen group.
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 as a substituent which may have.
The acyl group which may have a substituent is preferably an acyl group having 1 to 10 carbon atoms as an alkyl group, and hydrogen or a halogen group as a substituent which may have.
The alkoxy group which may have a substituent is preferably a linear alkoxy group having 1 to 5 carbon atoms as the alkyl group, and hydrogen or a halogen group as the substituent which may have. 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 as the substituent which may have.
The phenyl group which may have a substituent is preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as the substituent which may have.
The optionally substituted arylene group is preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as the optionally substituted arylene group.
The heterocyclic ring which may have a substituent is preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, tetrahydrothiopyran as a heterocyclic ring, and hydrogen and a halogen group as a substituent which may have. , a linear alkyl group having 1 to 10 carbon atoms, and an alkoxy group are preferable.
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 linear chain having 1 to 10 carbon atoms as the substituent which may have. Alkyl groups and alkoxy groups are preferred.

In particular, diketopyrrolopyrrole dye derivatives represented by general formulas (101) and (102), which are dye derivatives having substituents represented by 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 with respect to 100 parts by mass of the pigment.

By adding a pigment derivative to the pigment and performing pigmentation treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the surface of the pigment. In comparison, the primary particles of the pigment can be made finer.

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

<Resin 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 one of the following (C1) to (C4).
(C1): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A vinyl polymer obtained by radical polymerization of part A and at least one ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having no hydroxyl group and ethylenically unsaturated monomers having a hydroxyl group. A dispersant comprising part B, wherein the vinyl polymer part B has a (meth)acryloyl group.
(C2): A dispersant represented by the following general formula (1).
General formula (1) (HOOC-) _m - ^R1 -(-COO-[- ^R3 -COO-] _n - ^R2 ) _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, t is (4 -m).)
(C3): A dispersant containing an ethylenically unsaturated monomer having a phosphoric acid group or a sulfonic acid group and another ethylenically unsaturated monomer as copolymer components.
(C4): A polyester having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A dispersant (C4-1) comprising a portion A and a vinyl polymer portion B obtained by radically polymerizing one or more ethylenically unsaturated monomers.

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

(Dispersant of (C2)) A 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)) Dispersant (A) described in JP-A-2009-185277, and preferably further contains vinyl resin (B) having a tertiary amino group described in the same publication.

(Other resin-type dispersants)
A known resin-type dispersant other than the 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 added colorant and a site compatible with the colorant carrier. Specific examples include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids ( Part) Amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and liberation Oil-based dispersants such as amides and salts thereof formed by reaction with a polyester having a carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, Water-soluble resins such as styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used. 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 BYK-Japan. or Anti-Terra-U, 203, 204; 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 360, 340500, 340000, 340000 8500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401 manufactured by BASF , 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, and Ajinomoto Fine-Techno Co., Inc. Ajisper PA111, PB711, PB821, PB822, PB824, and the like. The resin-type dispersant used in the present invention is a resin-type dispersant having a carboxyl group.

The resin-type dispersant is preferably used in an amount of about 3 to 200% by weight, more preferably in an amount of about 5 to 100% by weight, based on the total amount of the coloring agent.

<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 range of 400 to 700 nm is used. Binder resins are classified into thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc., when classified according to their main curing methods, and active energy ray-curable resins are thermoplastic resins. It may be a resin or one having a thermosetting function, and an alkali-soluble resin is preferable from the viewpoint of developability. It may also contain a thermoplastic resin that is not curable with active energy rays, and it is also preferably alkali-soluble. These may be used alone or in combination of two or more.

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

<Thermoplastic resin>
Examples of thermoplastic resins that can be used as binder resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, 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 resins.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfone groups. Specific examples of resins include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrenesulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/ (anhydrous) maleic acid copolymer and the like. Among them, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly alkali-soluble resins having acidic groups and/or hydroxyl groups, has good developability, heat resistance, and transparency. Since it is high, it is preferably used.

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

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

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

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate. , and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

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

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. I don't mind. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. It is also possible to hydrolyze the group. Moreover, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

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

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

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

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

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

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

general formula (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 optionally having a benzene ring. is an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

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

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

Phosphate ester group-containing ethylenically unsaturated monomers can also be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide and polyphosphoric acid. is mentioned.

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

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

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

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

<Thermosetting compound (E)>
In the present invention, a thermosetting compound (E) can be used in combination with the thermoplastic resin as the binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by containing a thermosetting compound, it reacts during baking of the filter segment and increases the crosslink density of the coating film, so that the heat resistance of the filter segment is improved. As a result, pigment agglomeration during baking of the filter segment is suppressed, and the effect of improving the contrast ratio is obtained.

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

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

Commercially available products include, for example, Epicoat 807, Epicot 815, Epicot 825, Epicot 827, Epicot 828, Epicot 190P, Epicot 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicot 1004, Epicot 1256 (the above is a product 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 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (these are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (these are 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: manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.
and the like, but are not limited to these.

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

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

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

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

As the oxetane group having a functionality of two or more,
Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (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, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (e.g., oxetane-modified phenols described in Japanese Patent No. 3783462 Novolac resins, etc.) and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30. Such polymers can be obtained using known polymerization methods.

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

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

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

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

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

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth) Acrylates, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6 - hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate ) acrylate, tricyclodecanyl (meth)acrylate, methylolated melamine (meth)acrylate, epoxy (meth)acrylate, urethane acrylate and other acrylic and methacrylic acid esters, (meth)acrylic acid, styrene, Vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but not necessarily limited to these isn't it.

These commercially available products include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO- 303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, and Aronix 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, Viscoat #310HP, #335HP, #700, #295 manufactured by Osaka Organic Co., Ltd. , #330, #360, #GPT, #400, #405, NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like can be preferably used.

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

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

As these commercially available products, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toa Gosei 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 polyfunctional obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth)acrylate having a hydroxyl group. urethane acrylate and the like.

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

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

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

The above photopolymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

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

<Photoinitiator (G)>
The photosensitive composition of the present invention contains a photoinitiator (G). By containing the photopolymerization initiator (G), the composition can be cured by ultraviolet irradiation and the filter segment can be formed by photolithography. It is preferable to add a photopolymerization initiator (G) to prepare a solvent-developable or alkali-developable photosensitive composition.

As the photopolymerization initiator (G), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) Phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Acetophenone compounds such as; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2- Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl )-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)- Triazine compounds such as 6-triazine or 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-( O-benzoyloxime)], or oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.
These photopolymerization initiators can be used singly or as a mixture of two or more at an arbitrary ratio as required.

Commercially available acetophenone compounds include "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 the phosphine compounds are all "Omnirad 819" (bis(2,4, 6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and the like.

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

(Oxime ester compound)
In oxime ester-based compounds, absorption of ultraviolet rays causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the UV transmittance of the coating film may be low and the degree of curing of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. be. More preferably, it is an oxime ester photopolymerization initiator represented by the general formula (3).

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

In 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, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group , an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, 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 -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent); etc. is preferable.

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

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

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

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

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

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

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

Examples of the optionally substituted heterocyclic group for Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms containing a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho[2,3-b]thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group , 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanylyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH- carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsazinyl group, isothiazolyl group, phenothiazinyl group , isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group , morpholinyl group, thioxanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group and the like, but are limited to these. not a thing

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

Examples of the optionally substituted alkylsulfanyl group for Y ¹ include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and specific examples thereof include a methylthio group. , ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, etc., but not limited thereto.

Examples of the optionally substituted arylsulfanyl group for Y ¹ include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2- A naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group and the like may be mentioned, but are not limited to these.

The optionally substituted alkylsulfinyl group for Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples thereof 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, etc. Examples include, but are not limited to.

The optionally substituted arylsulfinyl group for 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 group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group , 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylamino Examples include, but are not limited to, a phenylsulfinyl group.

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

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

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

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

Examples of the amino group which may have a substituent for 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. mentioned.

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

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

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

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

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

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

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

The sulfamoyl group which may have a substituent for Y ¹ includes 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. groups, N,N-dialkylsulfamoyl groups, N,N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamoyl groups, and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group. famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylamino phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,N-dimethylsulfamoyl group group, N,N-dibutylsulfamoyl group, N,N-diphenylsulfamoyl group and the like, but are not limited thereto.

an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy 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 are alkenyl groups optionally having substituents for R1 described above, and having substituents. optionally substituted alkyl group, optionally substituted alkyloxy group, optionally substituted aryloxy group, optionally substituted heterocyclic ring 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 optionally substituted arylsulfinyl group, an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted acyloxy group, and It is synonymous with an optionally substituted amino group.

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

Among the oxime ester photopolymerization initiators represented by the general formula (3), the oxime ester photopolymerization initiators represented by the following general formula (4) or (5) have excellent sensitivity and are more preferable. be.

[Oxime ester photopolymerization initiator represented by general formula (4)]
general formula (4)

General formula (4) corresponds to the case where Z in general formula (3) is a —CO— group, Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ⁶ are hydrogen atoms or substituents. An alkyl group or an aryl group, which may have, is preferred. The optionally substituted alkyl group or optionally substituted aryl group for Y ⁴ to Y ⁶ is the same as the alkyl group or aryl group for Y ¹ and Y ² .

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

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

More preferred substituents of ^Y2 are cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclooctadecyl groups.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (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 It is synonymous with the substituent in ² .

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

When Z in general formula (5) is a direct bond, an oxime ester photopolymerization initiator represented by general formula (5a) below is preferred.

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

General formula (5a) corresponds to the case where Z in 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 are hydrogen atoms.
Moreover, 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 which may further have a substituent, such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group. A benzoyl group which may have a substituent or a nitro group is more preferred. Y ¹⁴ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group.

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

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

Specific examples of the oxime ester 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 general formula (5) is a --CO-- group, an oxime ester photopolymerization initiator represented by general formula (5b) below is preferred.

general formula (5b)

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

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

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

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

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

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

These sensitizers can be used singly or as a mixture of two or more at any ratio as required.
Commercially available products include "KAYACURE DETX-S" (2,4-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), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

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

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

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

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

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

Also, the content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0%, of the total solid content of the coloring composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, tapered 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 due to diffracted light from a mask during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing curing from progressing outside a desired pattern due to chain polymerization by photosensitivity.

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

<Ultraviolet absorber (K)>
The photosensitive coloring composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and includes benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylate-based organic compounds, cyanoacrylate-based organic compounds, and salicylates. Examples include organic compounds.

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

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

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

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

Examples of benzotriazole-based organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy -5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1- dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3- (2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1, 1,3,3-tetramethylbutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3, 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert -butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro -2H-benzotriazol-2-yl)phenyl]propionate. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

More specifically, TINUVIN P, PS, 234, 326 manufactured by BASF Corporation
, 329, 384-2, 900, 928, 99-2, 1130, ADEKA Co., Ltd. ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, Chemipro Kasei Co., Ltd. KEMIISORB71, 73, 74, 79 , 279, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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

More specifically, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TIN manufactured by BASF
UVIN 400, 405, 460, 477, 479, 1577ED, ADEKA Adekastab LA-46, LA-F70, Sun Chemical CYASORB UV-1164
etc.

Benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 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, KEMISORB 10, 11, 11S manufactured by Chemipro Kasei Co., Ltd.,
12, 111, SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., ADE Co., Ltd.
Adekastab 1413 manufactured by KA Corporation, UV-12 manufactured by Sun Chemical Co., Ltd., and the like can be mentioned.

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

<Antioxidant (L)>
The photosensitive coloring composition of the invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from oxidizing and yellowing due to thermal curing and thermal processes during ITO annealing. can be higher. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component is reduced, so measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator cause yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and to obtain a high transmittance of the coating film.

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

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

Hindered phenol antioxidants include 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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, 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-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-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-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3 ,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthio methyl)-o-cresol, 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, etc. is mentioned. 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 Co., Ltd., K manufactured by Chemipro Co., Ltd.
EMINOX101, 179, 76, 9425, IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Corporation, 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, a polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-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-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5, Ester of 5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino} -1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4 decanedioate -piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1,1dimethyl ethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl 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 ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like . In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

More specifically, Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87 manufactured by ADEKA Co., Ltd. , LA-402F, LA-502XP, Chemipro Kasei Co., Ltd. KAMISTAB29, 62, 77, 94, BASF Co., Ltd. Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100, Sun Chemical Co., Ltd. Cyasorb UV-3346, UV- 3529, UV-3853 and the like.

Phosphorus antioxidants include di(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2′-methylenebis(4,6- di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'- Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)-4 ，
4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' isopropyl Redenediphenol 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-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite Phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4 -di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

More specifically, Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Corporation, HostanoxP- manufactured by Clariant Chemicals Co., Ltd. EPQ etc. are mentioned.

Sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 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 specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd., and the like.

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

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

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

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

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

Fluorinated surfactants include surfactants or leveling agents having a fluorocarbon chain.

More specifically, AGC Seimi Chemical Co., Ltd. Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC Corporation Megafac F-253, F-477 , F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS -21, Sumitomo 3M Co., Ltd. FC-4430, FC-4432, Mitsubishi Materials Electronic Chemicals Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1, Neos Co., Ltd. Ftergent 602A, and the like.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl Ethers, polyoxyalkylene alkyl ethers, polyoxyphenylene distyrenated phenyl ethers, polyoxyethylene tribenzylphenyl ethers, polyoxyethylene polyoxypropylene glycols, polyoxyalkylene alkenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene alkyls Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitate tetraoleate , glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanol Amides, alkyl imidazolines and the like can be mentioned.

More specifically, Kao Corporation 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, Rheodor 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), Amit 102, 105, 105A, 302 , 320, Aminone PK-02S, L-02, Homogenol L-95, Adeka Pluronic L-23 manufactured by ADEKA Co., Ltd., 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd. (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 and the like.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

More specifically, acetamine 24, coatamine 24P, 60W, 86P conc, etc. manufactured by Kao Corporation can be mentioned.

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

More specific examples include Futergent 100 and 150 manufactured by Neos Co., Ltd., ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E and EC-8600 manufactured by ADEKA Corporation.

Amphoteric surfactants include lauramidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkylbetaines such as alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

More specifically, Amphithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N and the like manufactured by Kao Corporation can be mentioned.

When a surfactant is contained in the photosensitive coloring composition of the present invention, the amount of the surfactant added 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. Within this range, the coating properties of the coloring composition, the pattern adhesion, and the transmittance are well balanced.
The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

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

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

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

<Method for producing colored composition>
The coloring composition included in the present invention is obtained by dispersing a pigment in a dispersant, a binder resin and/or a solvent, preferably together with a dispersing aid (pigment derivative or surfactant), a kneader, a two-roll mill, and a three-roll mill. It can be manufactured by finely dispersing using various dispersing means such as a roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor. At this time, two or more pigments may be simultaneously dispersed in the colorant carrier, or separately dispersed in the pigment carrier may be mixed.

<Dispersed particle size of pigment>
The average dispersed particle size of the pigment in the coloring composition is preferably in the range of 30-200 nm. More preferably, it is in the range of 40-120 nm. In this range, the viscosity and dispersion stability are high, and when the coloring composition is used alone or mixed, and a photopolymerization material is added, not only the viscosity and dispersion stability, but also the sensitivity and the development speed are high. It is possible to obtain a colorant coloring composition, and when a color filter is produced using it, a high-quality color filter can be obtained.

As a method for measuring the dispersed particle size of the pigment, a Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs the dynamic light scattering method (FFT power spectrum method), is used. For example, D50 is the average diameter. It is preferable to use the solvent used for the dispersion as the diluting solvent for the measurement, and to measure the ultrasonically treated sample immediately after the sample preparation, because it is easy to obtain results with little variation.

<Method for producing a photosensitive coloring composition>
Moreover, when it is used as a photosensitive coloring composition, it can be prepared as a solvent-developable or alkali-developable coloring composition. Solvent-developable or alkali-developable colored composition comprises the colored composition, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally 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 in order to facilitate the formation of a colored film by coating it on a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

As the solvent, a solvent commonly used in the field can be used. Considering the performance such as boiling point, SP value, evaporation rate, viscosity, etc., it can be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). used in combination.

Solvents used include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-) , ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (solvents containing OH in the molecule solvents that do not contain -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Ester solvents 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, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Ether solvents 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, diethylene glycol methyl ethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, methylanisole and the like.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 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 Glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol diacetate and the like.

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. etc.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and the like.

Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

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

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

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

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

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

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

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

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

The color filter of the present invention is laminated with a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is attached to the substrate. A color liquid crystal display device is manufactured by laminating the film to the outside of the film. This color liquid crystal display device has Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA), Optically Convened Bend (OCB). ) can be used in a liquid crystal display mode in which coloration is performed using a color filter.

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

<Liquid crystal display device>
A liquid crystal display device having the color filter of the present invention will be described.
A liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC 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). On the inner surface of the first transparent substrate 11,
A TFT (thin film transistor) array 12 is formed, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . 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 that make up color filter 22 are separated by a black matrix (not shown).

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

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

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED. λ3), has a wavelength (λ4) at which the emission intensity is maximum within 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 wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, 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 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

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

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

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively. Examples 1 to 8, 14, 18 to 26, 32, 36 to 56, 104, 108, 116 to 118, 121 , 122, 201 to 208, 214, 218 to 226, 232, 236 to 256, 260, 264, 273, 274 , 277-280 are reference examples.

Prior to Examples, each measuring method will be described.

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

(Dispersion particle size measurement)
Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs the dynamic light scattering method (FFT power spectrum method), was used. The solvent used for the dispersion was used as the diluent solvent for measurement, and the sample treated with ultrasonic waves was measured immediately after sample preparation.

In addition, the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH/g
) are as follows:

(Average molecular weight of resin)
The number average molecular weight (Mn) and 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 "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min.
The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalent values.

<Acid value of resin (mgKOH/g)>
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution and stir to dissolve uniformly. ) to measure the acid value (mgKOH/g) of the resin solution. 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.

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

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

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

式（２０）

formula (20)

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

(Diketopyrrolopyrrole pigment 4)
Except for changing 60.9 parts of 4-cyanobiphenyl to 68.7 parts of N-butyl-4-cyanobenzamide, the same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out, and diketopyrrolopyrrole pigment 4 was obtained at 87.0 parts. I got it.

(Diketopyrrolopyrrole pigment 5)
Except for changing 60.9 parts of 4-cyanobiphenyl to 75.5 parts of N-phenyl-4-cyanobenzamide, the same procedure as in the production of diketopyrrolopyrrole pigment 2 was carried out, and 86.9 parts of diketopyrrolopyrrole pigment 5 were obtained. I got it.

(Diketopyrrolopyrrole pigment 6)
Except for changing 60.9 parts of 4-cyanobiphenyl to 87.8 parts of N,N-dibutyl-4-cyanobenzamide, diketopyrrolopyrrole pigment 2 was produced in the same manner as diketopyrrolopyrrole pigment 6, and 87 parts of diketopyrrolopyrrole pigment 6 .1 copy was obtained.

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

式（２１）

Equation (21)

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

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

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

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

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

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

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

(Production of finely divided pigment (A-8))
Diketopyrrolopyrrole Pigment 1 was obtained from commercially available C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) was used in the same manner as in the production of the micronized pigment (A-1), and the diketopyrrolopyrrole-based micronized pigment (A- 8) Obtained 97.3 parts.

(Refined pigment A-9 to 13)
Finely divided aluminum phthalocyanine pigments (A-9 to 13) of the following formulas 51 to 55 were prepared according to the examples of JP-A-2017-111398. The structure is shown below.

(Refined Pigment A-9)
Equation (51)

(Refined Pigment A-10)
Equation (52)

(Refined Pigment A-11)
Equation (53)

(Refined Pigment A-12)
Equation (54)

(Refined Pigment A-13)
Equation (55)

(Refined pigment (A-14))
phthalocyanine green pigment C.I. I. 100 parts of Pigment Green 58 (“FASTGEN GREENA 110” manufactured by DIC), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water and stirred for 1 hour while heating to 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. Thus, 97 parts of a modified pigment (A-14) was obtained.

(Refined pigments (A-15 to 17))
Finely divided quinophthalone pigments (A-15 to 17) of the following formulas (56) to (58) were prepared according to the examples of JP-A-2012-226110. Its structure is shown below.

(Refined Pigment A-15)
Equation (56)

(Refined Pigment A-16)
Equation (57)

(Refined Pigment A-17)
Equation (58)

(Refined pigment (A-18))
C. I. Pigment Yellow 138 (PY138) (BASF "Pariotol Yellow K0960-HD") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts are charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. for 6 hours. Kneaded. This mixture was poured into 2,000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent. A modified pigment (A-18) was obtained.

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

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

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

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

<Dye 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 type dispersant (C1))
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of monobutyltin oxide as a catalyst in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. was charged and purged with nitrogen gas, followed by reaction at 120° C. for 5 hours (first step). It was confirmed by acid value measurement 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 Parts, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of 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). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged. The reaction was continued until disappearance of the -1 peak was confirmed (third step). After confirming 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 with a solid content of 30%. The resulting dispersant had an acid value of 68, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

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

(Production of resin type dispersant (C3))
A separable 4-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and 1500 parts of cyclohexanone was charged. 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M-110") 120 parts, acid phosphooxyethyl methacrylate 6 parts, A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After 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 and 120 parts of ethyl acrylate are placed in a reaction tank equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer. , and 40 parts of methoxypropyl acetate were charged and purged 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. It was added every 30 minutes, reacted at 80° C. for 12 hours, and it was confirmed by measuring the solid content that 95% had reacted. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst are added and heated at 120° C. for 2 hours. The reaction was carried out 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 per solid content of 44 mgKOH/g was obtained. Furthermore, by adjusting the solid content with propylene glycol monomethyl ether acetate, a dispersant (C4-1) solution with a solid content of 30% was obtained. 133 parts of methoxypropyl acetate was introduced into a reactor 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 added to a dropping tank, stirred until uniform, and then reacted. It was added dropwise to the tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a vinyl resin (C4-2) having a tertiary amino group and a number average molecular weight of 2,500 (Mn) and an amine value per solid content of 345 mgKOH/g was obtained. A dispersant (C4-2) solution having a solid content of 30% was obtained by adjusting the solid content with propylene glycol monomethyl ether acetate.

<Production example of binder resin (D)>
(Preparation of binder resin (D-1) liquid)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, the mixture was added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 20.7 and 1.1 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (D-1) liquid was prepared by adding acetate. 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 separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the total amount of the copolymer solution obtained was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the non-volatile content. to prepare a binder resin (D-2). The weight average molecular weight (Mw) was 18,000.

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

(Preparation of binder resin (D-4) liquid)
A separable flask equipped with a cooling pipe was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate 40 parts, methacrylic acid 40 parts, methacrylic acid Prepare a mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (Nippon Oil & Fats Co., Ltd. "Perbutyl O"), and 40 parts of propylene glycol monomethyl ether acetate, and add a chain transfer agent dropping tank. As a solution, 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate were thoroughly stirred and mixed.
A reactor was charged with 395 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and heated in an oil bath with stirring to raise the temperature of the reactor to 90°C. After the temperature of the reactor was stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropping was carried out over 135 minutes while maintaining the temperature at 90°C.
After 60 minutes from the completion of dropping, the temperature of the reactor was raised to 110°C. After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen=5/95 (volume ratio) was started. The reactor was then charged with glycidyl methacrylate 7.
0 parts, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol),
0.8 part of triethylamine was added and reacted at 110° C. for 12 hours. Then, 150 parts of propylene glycol monomethyl ether acetate is added and cooled to room temperature, and about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to 20% by weight to obtain a binder resin (D-4) liquid. The weight average molecular weight of the resin was 18000, and the acid value per solid content was 2 mgKOH/g.

<Method for producing colored composition (single color)>
[Example 1]
(Preparation of colored composition (R-1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.), the pore size is 5.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (R-1) having a nonvolatile 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 liquid): 2.0 parts Binder resin (D-1: non-volatile 20% liquid): 16.0 parts Solvent (P): 61.5 parts

[Examples 2 to 56, Comparative Examples 1 to 3] (Preparation of colored compositions (R-2 to 59))
Colored compositions (R-2 to 59) were prepared in the same manner as in Example 1, except that the material types and weights were changed as described in Table 2. Table 2 shows the dispersed particle size of each.

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

[Examples 102 to 124, Comparative Examples 101 to 103] (Preparation of colored compositions (X-2 to 27))
A coloring composition (X-2 to 27) was prepared in the same manner as in Example 101, except that the material species and mass were changed as described in Table 3.

<Evaluation of coloring composition>
The obtained colored compositions (R-1 to 59, X-1 to 27) were tested for viscosity and storage stability by the following methods. Table 4 shows the results of the test.

<Measurement of viscosity characteristics>
An E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at a rotation speed of 20 rpm. The rank of evaluation is as follows.
○: Viscosity 4.0 or more and less than 20.0: Good level ×: Viscosity 20 or more: Level not suitable for practical use

(Storage stability>
The storage stability of the colored compositions obtained in Examples and Comparative Examples was evaluated by the following method.
The initial viscosity the day after the colored composition was prepared and the viscosity over time accelerated at 40 ° C. for 1 week were measured at 25 ° C. using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Measurement was performed under the condition of a rotation speed of 50 rpm. Based on the values of the initial viscosity and viscosity over time, the rate of change in viscosity over time was calculated according to the following formula, and the storage stability was evaluated in two stages.
[Rate of viscosity change over time] = | ([initial viscosity] - [viscosity over time]) / [initial viscosity] | × 100
○: Change rate less than 10% ×: Change rate 10% or more

<Method for producing a photosensitive coloring composition>
[Example 201]
(Photosensitive coloring composition (Y-1))
The following raw materials are mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y
-1) was obtained.
Coloring composition (X-1: non-volatile content 20%): 50.0 parts binder resin (D-2: non-volatile content 20%): 15.0 parts thermosetting compound (E-1): 1.0 parts heat Curable compound (E-2): 1.0 parts 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 Ultraviolet absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M : Non-volatile content 3%): 1.0 parts Storage stabilizer (N): 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 26.0 parts

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

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

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

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

(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.)]
The above (F-1) to (F-7) were mixed in equal amounts to obtain a photopolymerizable monomer (E).

<Photoinitiator (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 (manufactured by Ciba Japan)]
(G-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(G-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(G-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H
-carbazol-3-yl],1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by 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)]
The above (G-1) to (G-8) were mixed in equal amounts to obtain a photopolymerization initiator (G).

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

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

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

<Ultraviolet absorber (K)>
(K-1) 2-[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)]
The above (K-1) and (K-2) were mixed in equal amounts to obtain an ultraviolet absorber (K).

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

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

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

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

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

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. The results of the tests are shown in Table 6.

<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. After cooling the substrate to room temperature, it was exposed to ultraviolet light through a photomask using an extra-high pressure mercury lamp. Thereafter, the substrate was developed by spraying with an aqueous solution of sodium carbonate at 23° C., washed with deionized water, air-dried, and post-baked at 230° C. for 30 minutes in a clean oven to form stripes on the substrate. A colored pixel was formed.
The sensitivity of the colored composition was evaluated based on the minimum irradiation exposure amount at which the formed pattern of colored pixels was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: Less than 100 mJ/cm ² △: 100 or more and less than 150 mJ/cm ² ×: 150 mJ/cm ² or more

<Development speed evaluation>
The coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70° C. for 20 minutes.
2 ml of a 2% by weight potassium hydroxide aqueous solution was added dropwise to the coating film, and the time until the coating thickness was dissolved was measured to evaluate the development rate of the colored composition. The rank of evaluation is as follows.
○: Less than 10 seconds △: 10 seconds or more and less than 15 seconds ×: 15 seconds or more

<Measurement of viscosity characteristics>
An E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) was used to measure the viscosity at a rotation speed of 20 rpm.
The rank of evaluation is as follows.
○: Viscosity 2.0 or more and less than 10.0: Good level ×: 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 on the next day after preparing the photosensitive coloring composition and the viscosity over time accelerated at 40 ° C. for 1 week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). It was measured under the condition of 50 rpm at ℃. Based on the values of the initial viscosity and viscosity over time, the rate of change in viscosity over time was calculated according to the following formula, and the storage stability was evaluated in two stages.
[Rate of viscosity change over time] = | ([initial viscosity] - [viscosity over time]) / [initial viscosity] | × 100
○: Change rate less than 10% ×: Change rate 10% or more

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 coloring composition comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and a binder resin (D),
The pigment (A) is at least one selected from the group consisting of aluminum phthalocyanine pigments and quinophthalone pigments represented by the following formulas (56) to (58), and has an average primary particle diameter of 10 to 80 nm, and , the resin-type dispersant (C) contains an acidic resin-type dispersant represented by (C1) or (C2) below,
A coloring composition, wherein the coloring composition has an average dispersed particle size of 30 to 200 nm.
(C1): Polyester having a casil group, obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. A vinyl polymer obtained by radical polymerization of part A and at least one ethylenically unsaturated monomer selected from the group consisting of ethylenically unsaturated monomers having no hydroxyl group and ethylenically unsaturated monomers having a hydroxyl group. A dispersant comprising part B, wherein the vinyl polymer part B has a (meth)acryloyl group.
(C2): A dispersant represented by the following general formula (1).
General 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 from 1 to 50, t is (4 -m).)
Equation (56)

Equation (57)

Equation (58)

2. The coloring composition of claim 1, further comprising a dye. A photosensitive coloring composition comprising the coloring composition according to claim 1 or 2, 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 .

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