JP2020042242A - Photosensitive coloring composition for color filter, color filter, and liquid crystal display device - Google Patents

Abstract

To provide a photosensitive coloring composition for color filters, which offers superior film flatness, adhesivity, and solvent resistance, and to provide a color filter produced using the same, and a liquid crystal display device with such color filter.SOLUTION: The above challenge is cleared by providing a photosensitive coloring composition for color filters, comprising a colorant (A), binder resin (B), epoxy compound (C), photopolymerizable compound (D), photopolymerization initiator (E), and solvent (F), the colorant (A) containing a pigment represented by a chemical formula (1).SELECTED DRAWING: Figure 1

Description

  The present invention provides a color liquid crystal display device, a photosensitive color composition for a color filter used for manufacturing a color filter used for a color image pickup tube element, etc., a color filter including a filter segment formed using the same, and The present invention relates to a liquid crystal display device having the color filter.

  The color filter is formed by arranging two or more kinds of fine strip-shaped filter segments having different hues in parallel (in a stripe) or intersecting with each other on a transparent substrate such as a glass substrate. Are arranged so that two or more types of fine filter segments different from each other are sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue.

  For the color filter, a photosensitive coloring composition (resist) obtained by dispersing a coloring agent in a photosensitive transparent resin solution, which is manufactured by the following method, is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and thereafter, if necessary, a treatment such as heating is performed. Thereby, the filter segment pattern of the first color is obtained. By performing the same operation as above, a filter segment pattern of another color is formed, and a color filter is completed.

  The liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate in the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display. By providing a color filter between the two polarizing plates, color display becomes possible, and it is used for televisions, personal computer monitors, smartphones and the like. For this reason, there is an increasing demand for color filters with higher contrast, higher brightness, higher resolution, and higher color reproduction, which is a recent trend.

  Higher color reproduction of displays has been focused on improving the color reproducibility of the backlight, but it is necessary to use very dark colors for the color filters in order to improve the color reproducibility. In such a case, the concentration of the colorant in the photosensitive coloring composition is increased, and there is a concern that the flatness and the solvent resistance of the film may be reduced.

  Also, filter segments are becoming finer year by year for higher resolution, and adhesion to the substrate becomes a problem. Since a liquid crystal display device having a color filter is used in various environments today, adhesion after a pressure cooker test (PCT) is one of the required characteristics.

  Documents 1 and 2 disclose a technique using a brominated diketopyrrolopyrrole pigment having high contrast and brightness in a red filter segment which is one of the three primary colors (red, green, blue; RGB) of a color filter substrate. However, there is no mention of the flatness and adhesion of the film, and there is a higher demand for solvent resistance than today.

JP 2013-14750 A JP 2012-212969 PR

  An object of the present invention is to provide a photosensitive coloring composition for a color filter having excellent film flatness, adhesion, and solvent resistance, a color filter formed using the same, and a liquid crystal display device including the color filter. It is in.

  As a result of intensive studies, the present inventors have found that the problem can be solved by a photosensitive coloring composition for a color filter containing a brominated diketopyrrolopyrrole pigment and an epoxy compound, and reached the present invention.

That is, the present invention provides a color filter photosensitive composition comprising a colorant (A), a binder resin (B), an epoxy compound (C), a photopolymerizable compound (D), a photopolymerization initiator (E) and a solvent (F). The present invention relates to a coloring composition, wherein the coloring agent (A) contains the following chemical formula (1).

The present invention also relates to the photosensitive color composition for a color filter, further comprising a diketopyrrolopyrrole-based pigment represented by the following general formula (2).
[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbon atom of 1 12 alkyl group, an optionally substituted phenyl _{^{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, —CON (R ⁷ ) R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N (R ¹⁰ ) R ¹¹ , wherein R ^{1 to} R ¹¹ are each independently a carbon number. It is an alkyl group of 1 to 12, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not simultaneously become hydrogen atoms. Further, X is not A and B is a hydrogen atom, or X is B and A is not a hydrogen atom. ]

Further, in the present invention, the diketopyrrolopyrrole-based pigment represented by the general formula (2) may be any one of the following general formulas (2-1), (2-2), (2-3), And a photosensitive coloring composition for a color filter, comprising one or more pigments selected from the group consisting of the following general formula (2-4).

[In the general formulas (2-1), (2-2), (2-3) and (2-4), X represents a chlorine atom or a bromine atom. In the general formulas (2-3) and (2-4), R ^{12 to} R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl which may have a substituent. Group. R ¹³ and R ¹⁴ may combine to form an aromatic ring which may have a substituent.]

  Further, in the present invention, the epoxy compound (C) preferably has an epoxy equivalent of 100 to 400 (g / eq: molecular weight per epoxy group = molecular weight / number of epoxy groups). It relates to a coloring composition.

  In the present invention, the content of the epoxy compound (C) is from 0.1 to 15.0% by weight based on the weight of the solid content of the photosensitive coloring composition for a color filter. The present invention relates to a photosensitive coloring composition for a filter.

  The present invention also relates to a color filter including a substrate and a filter segment formed from the photosensitive coloring composition for a color filter.

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

  According to the present invention, a photosensitive coloring composition for a color filter having excellent film flatness, adhesion, and solvent resistance can be provided. By using the composition, a high-quality color filter and a liquid crystal display device can be provided.

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

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

<Colorant (A)>
(Diketopyrrolopyrrole pigment (Aa) represented by chemical formula (1))
In the photosensitive coloring composition for a color filter of the present invention, the coloring agent (A) contains the following chemical formula (1).

(Diketopyrrolopyrrole pigment represented by general formula (2) (Ab))
The photosensitive coloring composition for a color filter of the present invention preferably further contains a diketopyrrolopyrrole-based pigment represented by the general formula (2).

[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbon number of 1 To 12 alkyl groups, a phenyl group which may have a substituent, -CF3, -OR1, -SR2, -N (R3) R4, -COOR5, -CONH2, -CONHR6, -CON (R7) R8,- SO2NH2, -SO2NHR9, or -SO2N (R10) R11, wherein R1 to R11 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or a substituent Is an aralkyl group which may have However, A and B do not simultaneously become hydrogen atoms. X is not A and B is a hydrogen atom, or X is B and A is not a hydrogen atom. ]

  The alkyl group having 1 to 12 carbon atoms may be linear or branched, and specifically, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl Group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, and the like, but are not limited thereto. Absent.

  Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl group having 1 to 4 carbon atoms. And a phenyl group having a substituent such as a group. More specifically, phenyl, p-methylphenyl, 4-tert-butylphenyl, p-nitrophenyl, p-methoxyphenyl, p-chlorophenyl, 2,4-dichlorophenyl, 3-carbamoyl Examples include, but are not limited to, phenyl groups.

  Examples of the aralkyl group optionally having a substituent include a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4- Examples include, but are not limited to, a dichlorobenzyl group.

In the present invention, the diketopyrrolopyrrole-based pigment represented by the general formula (2) includes the following general formula (2-1), the following general formula (2-2), the following general formula (2-3), and It is preferably at least one pigment selected from the group consisting of the general formula (2-4). Thereby, the brightness, the contrast, and the crystal precipitation suppressing effect are further improved. In addition, R ^{12 to} R ¹⁴ in the general formulas (2-3) and (2-4) each represent an alkyl group having 4 or more carbon atoms or a phenyl group which may have a substituent. It is preferable from the viewpoint of the suppression effect. The reason why they exhibit high contrast and the effect of suppressing crystal precipitation is that steric hindrance effect of bulky substituents such as carboamide group having alkyl group having 4 or more carbon atoms, phenyl group, t-butyl group, etc. It is considered that the aggregation of is suppressed. Further, since the specific heterodiketopyrrolopyrrole pigment having a carboxamide group, a phenyl group, and a t-butyl group has excellent color characteristics, the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) is excellent. There is no loss of brightness.

[In the general formulas (2-1), (2-2), (2-3) and (2-4), X represents a chlorine atom or a bromine atom. In the general formulas (2-3) and (2-4), R ^{12 to} R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl which may have a substituent. Group. R ¹³ and R ¹⁴ may combine to form an aromatic ring which may have a substituent.]

  Specific examples of the specific heterodiketopyrrolopyrrole-based pigment represented by the general formula (2) that can be used in the present invention are shown below, but are not limited thereto.

(Other diketopyrrolopyrrole pigments (Ac))
The photosensitive coloring composition for a color filter of the present invention contains, as a colorant (A), a diketopyrrolopyrrole-based pigment (A-a) and a diketopyrrolopyrrole-based pigment (A-) as long as the effects of the present invention are not impaired. Diketopyrrolopyrrole pigments (Ac) other than b) may be used in combination. Specifically, C.I. I. Pigment Red 254, 255, 264, 270, 272, 283, C.I. I. Diketopyrrolopyrrole-based pigments such as CI Pigment Orange 71, 73, or 81 can be used, but are not limited thereto. Diketopyrrolopyrrole pigments that can be used in combination include C.I. I. Pigment Red 254 is preferred. C. I. The reason why Pigment Red 254 is preferable is that the excellent lightness of the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) is not adversely affected.

(Method for producing diketopyrrolopyrrole pigment)
The brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) can be produced by a succinic diester synthesis method. That is, 2-mol of 4-bromobenzonitrile is added to 1 mol of succinic diester in an inert organic solvent such as tert-amyl alcohol at a high temperature of 80 to 110 ° C. in the presence of an alkali metal or an alkali metal alkoxide. A condensation reaction is performed to generate an alkali metal salt of a diketopyrrolopyrrole compound, and then, by protonating the alkali metal salt of the diketopyrrolopyrrole compound with water, an alcohol, an acid, or the like, A brominated diketopyrrolopyrrole pigment can be obtained. At this time, the size of the obtained primary particle diameter can be controlled by the temperature, the kind, the ratio, and the amount of water, alcohol or acid in the protonation. The method for producing the brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) is not limited to this method.

  Specific heterodiketopyrrolopyrrole-based pigments represented by the general formula (2) are described, for example, in the document Synth. Commun. , 1988, 18, 1213 and Tetrahedron, 58 (2002) 5547-5565.

  The specific heterodiketopyrrolopyrrole-based pigment represented by the general formula (2) is C.I. I. Pigment Red 254 or C.I. I. Pigment Red 291 can be synthesized. This can be achieved by using a method using at least two structurally different benzonitrile compounds in the succinic diester synthesis method (hereinafter, referred to as “succinic diester co-synthesis method”). Specifically, in the method described in WO2009 / 081930 pamphlet, a plurality of benzonitrile compounds to be used are 4-chlorobenzonitrile or 4-bromobenzonitrile and benzonitrile represented by the following chemical formula (3). By selecting from the compounds, the specific heterodiketopyrrolopyrrole-based pigment of the general formula (2) can be selected from C.I. I. Pigment Red 254 or C.I. I. Pigment Red 291.

Chemical formula (3)

[In the chemical formula (3), A and B each independently have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and a substituent. also a phenyl _{^{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, -CON (R 7) R 8, -SO 2 NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N (R ¹⁰ ) R ¹¹ , wherein R ^{1 to} R ¹¹ each independently have an alkyl group having 1 to 12 carbon atoms and a substituent. A phenyl group which may be substituted, or an aralkyl group which may have a substituent. However, A and B do not simultaneously become hydrogen atoms. ]

  The diketopyrrolopyrrole-based pigment of the present invention is obtained by separately producing a brominated diketopyrrolopyrrole pigment represented by the chemical formula (1) and a specific heterodiketopyrrolopyrrole-based pigment represented by the general formula (2). These can be mixed and used. Further, a specific heterodiketopyrrolopyrrole-based pigment synthesized by a succinic acid diester co-synthesis method and C.I. I. Pigment Red 254 can be further used by mixing with a brominated diketopyrrolopyrrole pigment represented by the chemical formula (1). In these cases, the pigments may be simply mixed before being dispersed, or may be pulverized and mixed by salt milling.

  In the diketopyrrolopyrrole pigment of the present invention, a brominated diketopyrrolopyrrole pigment represented by the chemical formula (1), a specific heterodiketopyrrolopyrrole pigment represented by the general formula (2), and C.I. I. The mass ratio of Pigment Red 254 can be analyzed using TOF-MASS, FD-MASS, LC-MASS, or NMR. Alternatively, as disclosed in JP-A-08-199085, a composition having a diketopyrrolopyrrole-based pigment is stirred with di-tert-butyl dicarbonate and 4-dimethylaminopyridine in tetrahydrofuran at room temperature. After converting into a soluble diketopyrrolopyrrole compound obtained by the above, analysis using NMR, MASS or LC-MASS may be performed. Alternatively, the above analysis may be performed after the hydrogen of the NH group of the pyrrolopyrrole ring is substituted with an alkyl group using an alkyl halide or the like and converted to a soluble diketopyrrolopyrrole.

(Other coloring agents (Ad))
The photosensitive coloring composition for a color filter of the present invention contains, as the colorant (A), diketopyrrolopyrrole-based pigments (Aa), (Ab) and (A-) as long as the effects of the present invention are not impaired. Coloring agents (Ad) other than c) may be used in combination. These colorants can be used alone or as a mixture of two or more at any ratio as needed.

  Examples of other coloring agents (Ad) include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 269, 273, 274, 276, 277, 278, 279, 280, 281, 282, And red pigments such as 284, 285, 286, 287. Further, azo pigments described in JP-A-2014-112527, azo pigments described in JP-A-2013-161046, and the like can be used.

  C.I. I. Orange pigments such as CI Pigment Orange 43 and / or 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, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231. In addition, quinophthalone pigments described in Japanese Patent No. 4993026 and the like can be mentioned.

  Preferred pigments used in combination include azo-based, naphthol-azo-based, anthraquinone-based, quinophthalone-based, and perylene-based pigments from the viewpoints of fastness such as heat resistance and light fastness and a chromaticity region. Specifically, C.I. I. Pigment red 177, 269, C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

  Further, 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. These derivatives may be in the form of lake pigments formed by dyeing a lake.

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

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

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

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

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

<Dye derivative>
The photosensitive coloring composition for a color filter of the present invention may optionally contain a dye derivative.

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

Specifically, examples of the diketopyrrolopyrrole-based dye derivatives include JP-A-2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP2017-156397, and phthalocyanine. JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-5573266, and anthraquinone-based pigment derivatives include JP-A-63-264677, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325, Kina JP-A-48-54128, JP-A-H03-9961, JP-A-2000-273383, and JP-A-2011-162662, and thiazineindigo as dioxazine-based dye derivatives. JP-A-2007-314785 as a dye derivative, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003 JP-A-168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, and JP-A-2003-167112 as a quinophthalone-based dye derivative Gazette, JP 2006-291194 A JP-A-2008-31281, JP-A-2012-226110, and JP-A-2012-208329 and JP-A-2014-5439 as naphthol-based dye derivatives; JP-A-172520, JP-A-2012-172092, as the acidic substituent, JP-A-2004-307854, and as the basic substituent, JP-A-2002-201377, JP-A-2003-171594, Known dye derivatives described in JP-A-2005-181383 and JP-A-2005-213404 are exemplified. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, and the like. The compound having a substituent such as a sex group has the same meaning as the dye derivative.

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

[Diketopyrrolopyrrole dye derivative]

[Phthalocyanine dye derivative]

[Anthraquinone dye derivative]

[Quinacridone dye derivative]

[Dioxazine dye derivative]

[Thiazine indigo dye derivative]

[Triazine dye derivative]

[Benzoisoindole dye derivative]

[Quinophthalone dye derivative]

[Naphthol dye derivative]

[Azo dye derivative]

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 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, A phthalimidoalkyl group which may have a group, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), and (158) ) Or (159). m and n each independently represent a positive integer. However, when one molecule has a plurality of substituents, one or more is a substituent other than a hydrogen atom. When only one substituent is present in one molecule, it is a substituent other than a hydrogen atom.

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

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

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

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

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

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

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

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

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

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

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

<Resin type dispersant>
Known resin-type dispersants can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant has a colorant affinity site having a property of adsorbing to the additive colorant and a site compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier. Any substance can be used as long as it functions to stabilize the polymer. Specific examples include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, and polycarboxylic acid (partial) amine. Salts, ammonium polycarboxylates, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic esters, and modified products thereof, poly (lower alkylene imines) and free carboxyl groups Oily dispersants such as amides and salts thereof formed by the reaction with a polyester having methacrylate, and (meth) acrylic acid-styrene copolymer , (Meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone and other water-soluble resins and water-soluble polymer compounds, polyesters, modified polyacrylates System, ethylene oxide / propylene oxide adduct, phosphate ester system, etc., and these can be used alone or in combination of two or more.
Examples of the polymer dispersant having a basic functional group include a nitrogen atom-containing graft copolymer and a nitrogen atom-containing functional group containing a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring in a side chain. Examples include an acrylic block copolymer and a urethane polymer dispersant.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by Big Chem Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bycumen, etc. OLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32,500, 32550, 33500, 32600, 34750, 35100, 36600, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by BASF, such as 38500, 41000, 41090, 53095, 55000, 56000, and 76500. , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 53, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajispa-PA111, PB711, PB821, PB822 manufactured by Ajinomoto Fine-Techno. , PB824 and the like.

In the photosensitive coloring composition of the present invention, a resin type dispersant having a carboxyl group can be suitably used. Examples of the shape of the resin-type dispersant having a carboxyl group include a linear resin-type dispersant and a comb-type resin-type dispersant.

[Comb-shaped resin-type dispersant 1 having a carboxyl group]
The comb-type resin-type dispersant 1 having a carboxyl group can be produced by a known method such as WO 2008/007776, JP-A-2008-029901, JP-A-2009-155406, and the like.
For example, a hydroxyl group of a polymer having a hydroxyl group and a resin-type dispersant which is a reaction product of an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group, and a tetracarboxylic dianhydride A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of the product with an acid anhydride group.

[Comb-shaped resin-type dispersant 2 having a carboxyl group]
The comb-shaped resin-type dispersant 2 having a carboxyl group is produced by a known method such as WO2008 / 007776, JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416. can do.
For example, in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tetracarboxylic dianhydride, a hydroxyl group, a t-butyl group or an oxetane skeleton, having a thermal crosslinking group such as a blocked isocyanate Resin-type dispersant obtained by reacting a resin-type dispersant having an ethylenically unsaturated monomer and a side chain obtained by polymerizing the other monomer and a thylene-type unsaturated monomer having an isocyanate group in the hydroxyl group of the side chain It is.

[Carboxyl group-containing linear resin dispersant]
The linear resin-type dispersant having a carboxyl group can be produced by a known method such as JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group is produced by adding a tricarboxylic anhydride to a hydroxyl group from a vinyl polymer having one hydroxyl group at one end as a raw material. Can be done.

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

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

  The content of the binder resin (B) in the photosensitive 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. It is preferably used in an amount of 20 parts by mass or more because of good film formability and various resistances, and is preferably used in an amount of 400 parts by mass or less because the colorant concentration is high and good color characteristics can be exhibited. .

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

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

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

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

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

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

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

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

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

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

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

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

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

General formula (4)

(In the general formula (4), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon atom which may have a benzene ring. It is an alkyl group of numbers 1 to 20, and q is an integer of 1 to 15.)

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

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

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

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

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

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

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is from 2,000 to 40,000, preferably from 3,000 to 30,000, and more preferably 4,000, in order to impart solubility in alkali development. It is more preferably from 20,000 to 20,000. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is reduced, and the exposure pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development is reduced, residues are generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg / g), preferably from 70 to 180, more preferably from 90 to 170 in order to impart alkali development solubility. Range. If the acid value is less than 50, the solubility in alkali development decreases, residues are generated, and the linearity of the pattern deteriorates. If it exceeds 200, the adhesion to the substrate will be reduced, and the exposure pattern will not remain easily.

[Thermosetting compound]
In the present invention, a thermosetting compound (excluding an epoxy compound (C) described later) can be further contained as a binder resin (B) in combination with a thermoplastic resin. When a color filter is produced using the photosensitive coloring composition of the present invention, by containing a thermosetting compound, it reacts at the time of firing of the filter segment and increases the crosslink density of the coating film, thereby improving the heat resistance of the filter segment. In addition, the effect of suppressing the aggregation of the pigment at the time of firing the filter segment and improving the contrast ratio can be obtained.

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

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

Examples of the monofunctional oxetane group include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, and 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.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

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

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

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

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

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

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

(Curing agent)
Further, the photosensitive coloring composition of the present invention may contain a curing agent (curing accelerator) and the like, if necessary, to assist the curing of the thermosetting compound. As a curing agent, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, and the like are effective, but are not particularly limited thereto, and can react with a thermosetting compound. Any curing agent may be used. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl- 4 Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S) -Triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct) and the like. . These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the thermosetting compound.

<Epoxy compound (C)>
The photosensitive coloring composition of the present invention contains an epoxy compound (C). 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 phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Phenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimethanol) Polycondensates with phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols with various aldehydes, alcohols Glycidyl Glycidyl ether-based epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based epoxy resin, etc. It is not limited. These may be used alone or in combination of two or more.

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

  The epoxy equivalent of the epoxy compound (C) is preferably 100 to 400 (g / eq: molecular weight per epoxy group = molecular weight / number of epoxy groups). When the epoxy equivalent is 100 g / eq or more, the cross-linking density of the film is not too high and the shrinkage during curing is small, so that the flatness of the film is good. When the epoxy equivalent is 400 g / eq or less, the curability is sufficient, and the effect of improving adhesion and solvent resistance increases.

  The amount of the epoxy compound (C) is preferably from 0.1 to 15.0% by weight based on the weight of the solid content of the photosensitive coloring composition for a color filter. When the amount is less than 0.1% by weight, the effect of improving adhesion and solvent resistance is reduced, and when the amount is more than 15.0% by weight, the developability of the photosensitive coloring composition may be deteriorated.

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

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

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

[Photopolymerizable compound having acid group]
The photopolymerizable compound (D) in the present invention may contain a photopolymerizable compound having an acid group. By using a photopolymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is alkali-developed, the solubility of the formed coating film in an alkali developing solution can be increased, and the developing speed can be improved. Residue can be reduced. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

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

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

[Photopolymerizable compound having urethane bond]
The photopolymerizable compound (D) in the present invention may contain a photopolymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. By containing a photopolymerizable compound having a urethane bond, deposition of a coloring material when the formed coating film is heated can be suppressed, and solvent resistance and adhesion to a substrate can be improved.

Examples of the polymerizable compound having a urethane bond include a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a polyfunctional isocyanate reacted with an alcohol, and further having a hydroxyl group (a ) Polyfunctional urethane acrylate obtained by reacting acrylate.

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

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

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

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

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

<Photopolymerization initiator (E)>
The photosensitive composition of the present invention contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E), the composition can be cured by irradiation with ultraviolet light, and a filter segment can be formed by photolithography. It is preferable that the composition is prepared in the form of a solvent-developing or alkali-developing photosensitive composition by adding a photopolymerization initiator (E).

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

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

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

[Oxime ester compound]
The oxime ester-based compound absorbs ultraviolet rays to cause cleavage of the N—O bond of the oxime, thereby generating an iminyl radical and an alkyloxy radical. These radicals are further decomposed to generate highly active radicals, so that a pattern can be formed with a small exposure dose. When the colorant concentration of the photosensitive coloring composition is high, the UV transmittance of the coating film is low and the degree of curing of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. You. More preferred are oxime ester-based photopolymerization initiators represented by the general formula (5).

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

In the general formula (5),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An 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 alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent) And the like.

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

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

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

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

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

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

The aryloxy group which may have a substituent in Y ¹ includes a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, a naphthyloxy group, and a 2-naphthyloxy group. 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 an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group , 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquino Ryl, quinolyl, phthalazinyl, naphthyridinyl, quinoxanilyl, quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazolyl, 2-carbazolyl, 3-carbazolyl, β-carbolinyl, phenanthridinyl, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenosadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, thioxanthryl 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

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

Examples of the optionally substituted alkylsulfanyl group for Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 20 carbon atoms. Specific examples include methylsulfinyl. Group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decylsulfinyl group, dodecylsulfinyl group, octadecylsulfinyl group Group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group and the like, but are not limited thereto.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Y ² may have a substituent, alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, a substituent An alkyloxy group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, A heterocyclic oxy group, an alkylsulfanyl group optionally having a substituent, an arylsulfanyl group optionally having a substituent, An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, Synonymous with an optionally substituted acyloxy group and an optionally substituted amino group.

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

  Among the oxime ester-based photopolymerization initiators represented by the general formula (5), the oxime ester-based photopolymerization initiators represented by the following general formula (6) or (7) are excellent in sensitivity and more preferable. is there.

[Oxime ester-based photopolymerization initiator represented by the general formula (6)]

The general formula (6) corresponds to the case where Y ³ in the general formula (5) is a Ph-S-Ph- group, and Y ⁴ to Y ⁶ are a hydrogen atom or an alkyl which may have a substituent. A group, an aryl group and an acyl group are preferred. The alkyl group which may have a substituent or the aryl group which may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or the aryl group in Y ¹ and Y ² . Z is a direct bond or a -CO- group.

[Oxime ester-based photopolymerization initiator represented by the general formula (6a)]
In the general formula (6a), Z in the general formula (6) corresponds to a —CO— group. Further, as Y ¹ , an aryl group which may have a substituent, as Y ² , an alkyl group having 1 to 20 carbon atoms which may have a substituent, and as Y ⁴ and Y ⁶ , a hydrogen atom is further added. More preferably, Y ⁵ is a hydrogen atom or a Y ⁷ —CO— group.

As Y ⁷ , for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group, an aryloxy group such as a p-tolyloxy 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, methacryloyl group, methoxalyl group Alkylsulfanyl groups such as acyl group, methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; methylamino groups and cyclohexylamino groups. Killamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, phenylamino group, arylamino group such as p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, etc. Alkyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, aryl group such as benzofuranyl group, furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, Carboxy, formyl, mercapto, sulfo, mesyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethylammonium Mill group, dimethylsulfonium group, And a triphenylphenacylphosphonium group.

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

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (6a) include the photopolymerization initiators represented by the above-mentioned chemical formulas (6a-1) and (6a-2).

[Oxime ester-based photopolymerization initiator represented by the general formula (6b)]
General formula (6b) corresponds to the case where Z in general formula (6) is a direct bond. The oxime ester-based photopolymerization initiator represented by the general formula (6b), preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent as ^{Y 1} and ^{Y 2,} the Y 4 to Y ⁶ At least one is preferably an acyl group which may have a substituent. Specifically, it is a photopolymerization initiator represented by the above chemical formula (6b-1) or (6b-2).

[Oxime ester-based photopolymerization initiator represented by the general formula (7)]

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

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

  When Z in the general formula (7) is a direct bond, the oxime ester-based photopolymerization initiator represented by the general formula (7a) is preferable.

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

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

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

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (7a) include the photopolymerization initiators represented by the chemical formulas (7a-1) to (7a-6).

"Oxime ester-based photopolymerization initiator represented by general formula (7b)"
When Z in the general formula (7) is a —CO— group, an oxime ester-based photopolymerization initiator represented by the general formula (7b) is preferable.

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

  Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (7b) include the photopolymerization initiators represented by the chemical formulas (7b-1) to (7b-4).

  Commercial products of these oxime ester compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyl oxime) (IRGACURE OXE01), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE02) (all manufactured by BASF), N-1919 (manufactured by ADEKA) , TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like. In addition, oximes described in JP-A-2007-21091, JP-A-2009-79619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photopolymerization initiator.

  The content of the photopolymerization initiator (E) is preferably 0.1 to 20 parts by mass, based on the total solid content of the photosensitive coloring composition (100 parts by mass), and is photocurable and developable. From the viewpoint, it is more preferably 0.5 to 10 parts by mass. If the amount is less than 0.1 part by mass, the adhesion of the formed pattern to the base material becomes poor, and if the amount exceeds 20 parts by mass, a problem may occur in the developability or a decrease in lightness after 230 ° C. heat treatment may occur. .

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of 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 oxanol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-bis (diethylamino) benzophenone and the like.

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

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

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

  The content when the sensitizer is used is preferably 2 to 60 parts by mass with respect to 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability. More preferably, it is 4 to 50 parts by mass.

<Solvent (F)>
The photosensitive coloring composition of the present invention is coated with a solvent (F) so as to easily form a colored film by coating on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm. To be included. The solvent is selected in consideration of not only good coatability of the photosensitive coloring composition but also solubility of each component and further safety.

As the solvent (F), a solvent usually used in the field can be used, and considering the properties such as the boiling point, the SP value, the evaporation rate, and the viscosity, appropriately according to the application conditions (speed, drying conditions, etc.). Used alone or in combination.

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

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

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

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-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.

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

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

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

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

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

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

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

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

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

Further, the content of the thiol-based chain transfer agent is preferably 0.05 to 10%, more preferably 0.1 to 8.0%, of the total solid content of the photosensitive coloring composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage, etc. are improved.

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

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

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

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

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

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

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

  2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy -5'-t-octylphenyl) benzotriazole, 5% of 2-methoxy-1-methylethyl acetate and 95% of benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-(1,1- Mixture of dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazol-2-yl -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1 , 3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-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-benzo) Liazol-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, 329, 384-2, 900, 928, 99-2, 1130, manufactured by BASF, and ADK STAB LA-29, LA-31RG, LA, manufactured by ADEKA Corporation. -32, LA-36, KEMIPROB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

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

  More specifically, KEMISORB 102 manufactured by Chemipro Kasei Co., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, ADK STAB LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. No.

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

  More specifically, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cipro Kasei Co., Ltd., ADK STAB 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sun Chemical Co., Ltd. No.

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

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

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

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

  Hindered phenolic antioxidants include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2-t -Butyl-5-methylphenol), stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-) (Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8, 1 -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-tert-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,6-bis (dodecylthiomethyl) ) -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] ethylene bisoxybisethylene, 1,6-hexanediol bis [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, -Dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol and the like. No. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

  More specifically, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, KEMINOX101, 179, 76 manufactured by Chemiplo Corporation, 9425, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, manufactured by BASF, Cyanox CY-1790, CY-2777, manufactured by Sun Chemical Co., Ltd. Is mentioned.

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

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

  Examples of the phosphorus-based antioxidants include di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2′-methylenebis (4,6- Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4′- Isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris (isodecyl) phosphite, triphenyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4-Biphenyldiphosphonite Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4′isopropylidenediphenolalkylphosphite, Trisnonylphenylphosphite, trisdinonylphenylphosphite, 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) Phosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite Diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonite) Loxy) -benzene, ethyl bisphosphite (2,4-ditert-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, and Hostanox P- manufactured by Clariant Chemicals Co., Ltd. EPQ and the like.

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

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

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

  When the content of the antioxidant is 0.5 to 5.0% by mass based on 100% by mass of the solid content of the photosensitive coloring composition, the transmittance, the spectral characteristics, and the sensitivity are more preferable.

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

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

More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345/346, 347, 348, 349, 370, 377, 378 manufactured by Big Chemie. , 3455, UV3510, 3570, Dow Corning Toray FZ-7002, 2110, 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, and KP-341.

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

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

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

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

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

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

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

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

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

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

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

<Storage stabilizer>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and 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 can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

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

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

<Method for producing photosensitive composition>
The photosensitive coloring composition included in the present invention is obtained by dispersing a colorant in a dispersant, a colorant carrier such as a binder resin and / or a solvent, preferably together with a dispersing aid (a dye derivative or a surfactant), It can be manufactured by finely dispersing using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). . At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of a coloring agent such as a dye is high, specifically, the solubility in a solvent to be used is high, and it is produced by dispersing finely as described above if it is dissolved by stirring and no foreign matter is confirmed. No need.

  When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developing or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent and other dispersing aids and additives. And the like 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.

<Dispersion aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a dye derivative, a dispersant, and a surfactant can be appropriately contained. Since the dispersing agent has a large effect of preventing the re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing agent has a lightness, contrast, and storage stability. The property becomes good. The dye derivative and the dispersant are as described above.

<Surfactant>
Examples of the surfactant include those described above for the leveling agent, and these can be used alone or in combination of two or more, but are not necessarily limited thereto.

  When a surfactant is added, the amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. If the amount of the surfactant is less than 0.1 part by mass, it is difficult to obtain the added effect, and if the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The photosensitive coloring composition of the present invention is obtained by means of centrifugation, filtration using a sintered filter or a membrane filter, or the like, with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more. It is preferable to remove particles and mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

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

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

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

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

  Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Alternatively, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. On the color filter of the present invention, an overcoat film, a transparent conductive film or the like is formed as necessary.

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

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

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

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

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

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

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

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

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

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

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

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

(Acid value of resin type dispersant and binder resin)
The acid value of the resin-type dispersant and the binder resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JIS K0070.

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

<Method of synthesizing diketopyrrolopyrrole pigment (A-a)>
Table 1 shows the structural formula of the diketopyrrolopyrrole-based pigment (Aa) synthesized below.
(Diketopyrrolopyrrole-based pigment (A-a))
Under a nitrogen atmosphere, 200 parts of tert-amyl alcohol dehydrated by molecular sieve and 140 parts of sodium-tert-amyl alkoxide were added to a stainless steel reaction vessel equipped with a reflux tube, and the mixture was heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask, and dissolved by heating to 90 ° C. while stirring to prepare a solution of these mixtures. A heated solution of this mixture was slowly dropped into the above-described alcoholate solution heated to 100 ° C. at a constant rate over 2 hours while stirring vigorously. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole-based compound. Further, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a glass-made reaction vessel equipped with a jacket, and cooled to -10 ° C. The cooled mixture was cooled to 75 ° C. while rotating a shear disk having a diameter of 8 cm at 4000 rpm using a high-speed stirring disperser, and the alkali metal salt of the diketopyrrolopyrrole compound obtained earlier was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole-based compound at 75 ° C while cooling so that the temperature of the mixture of methanol, acetic acid, and water always keeps a temperature of -5 ° C or less. , And was added in small portions over approximately 120 minutes. After the addition of the alkali metal salt, red crystals precipitated, and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C., and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to form a suspension having a methanol concentration of about 90%, and the mixture was stirred at 5 ° C. for 3 hours to perform particle sizing with crystal transition and washing. Subsequently, the aqueous paste of the diketopyrrolopyrrole-based compound obtained by filtration with an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to obtain a diketopyrrolopyrrole pigment (A-a) 150. 0.8 parts were obtained.

<Synthesis Method of Diketopyrrolopyrrole Pigment (Ab)>
Tables 1 to 3 show the structural formulas of the diketopyrrolopyrrole pigments (Ab_1 to 7) synthesized below.

(Diketopyrrolopyrrole-based pigment (Ab_1))
While putting 220 parts of tert-amyl alcohol in the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Then, 100 parts of tert-amyl alcohol, 85.0 parts of a compound of the following chemical formula (8) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in the reaction vessel 2. This was dissolved, and this was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., and 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol to obtain a diketopyrrolopyrrole-based pigment (Ab_1). One part was obtained.

Chemical formula (8)

(Diketopyrrolopyrrole pigment (Ab_2))
A diketopyrrolopyrrole-based pigment was prepared in the same manner as in the production of the diketopyrrolopyrrole-based pigment (Ab_1), except that 60.9 parts of 4-cyanobiphenyl was changed to 54.1 parts of 4-tert-butylbenzonitrile. (Ab_2) 83.9 parts were obtained.

(Diketopyrrolopyrrole pigment (Ab_3))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 68.7 parts of N-butyl-4-cyanobenzamide, the same procedure as in the preparation of the diketopyrrolopyrrole pigment (Ab_1) was carried out. 87.0 parts of a pigment (Ab_3) were obtained.

(Diketopyrrolopyrrole-based pigment (Ab_4))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 75.5 parts of N-phenyl-4-cyanobenzamide, it was carried out in the same manner as in the production of the diketopyrrolopyrrole pigment (Ab_1). 86.9 parts of a pigment (Ab_4) were obtained.

(Diketopyrrolopyrrole pigment (Ab_5))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, the same procedure as in the preparation of the diketopyrrolopyrrole-based pigment (Ab_1) was carried out. 87.1 parts of a pyrrole-based pigment (Ab_5) were obtained.

(Diketopyrrolopyrrole pigment (Ab_6))
While putting 220 parts of tert-amyl alcohol in the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added, and the mixture was heated and stirred at 90 ° C. Then, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following chemical formula (9) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl were heated in the reaction vessel 2. This was dissolved, and this was dropped into the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, the mixture was cooled to 60 ° C., and 400 parts of methanol and 50 parts of acetic acid were added, followed by filtration and washing with methanol to obtain a diketopyrrolopyrrole-based pigment (Ab_6). 8 parts were obtained.

Chemical formula (9)

(Diketopyrrolopyrrole pigment (Ab_7))
Except that 60.9 parts of 4-cyanobiphenyl was changed to 87.8 parts of N, N-dibutyl-4-cyanobenzamide, the same procedure as in the preparation of the diketopyrrolopyrrole-based pigment (Ab_6) was carried out. 87.1 parts of a pyrrole pigment (Ab_7) were obtained.

<Method for producing other diketopyrrolopyrrole-based pigment (Ac)>
(Red colorant (Ac))
C. I. Pigment Red 254 (“Irgafor Red B-CF” manufactured by BASF) was used as a coloring agent (Ac).

<Production method of red colorant>
The compositions of the red colorants (P-1 to 10) produced below are shown in Tables 1 to 3.

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

(Red colorant (P-2-10))
Hereinafter, red coloring agents (P-2 to 10) were obtained in the same manner as the red coloring agent (P-1), except that the composition and the amount were changed as shown in Tables 1 to 3.

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

<Production method of other coloring agent (Ad)>
Table 4 shows the pigment components of the other colorants (Ad_1 to 14) produced below.

(Colorant (A-d_1))
C. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by BASF): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded material is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing are repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. all day and night. Thus, a coloring agent (Ad_1) was obtained.

(Colorant (Ad_2))
C. I. Pigment Red 269 (“Toner Magenta F8B” manufactured by Clariant), 100 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. After drying, a colorant (Ad_2) was obtained.

(Colorant (Ad-3))
A coloring agent (Ad_3) represented by the following chemical formula (10) was obtained by a production method similar to that of the red coloring agent 1 (R-1) described in Examples of Japanese Patent No. 6350885.

Chemical formula (10)

(Colorant (Ad-4))
To 2000 parts of water, 30 parts of a resin 1 having a cationic group in a side chain in terms of a nonvolatile content were added, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. Meanwhile, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and added dropwise to the resin solution. After the dropwise addition, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was determined that a salt-forming compound was obtained, with the end point at which bleeding disappeared as the end point. After allowing to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and dried. I. A colorant (Ad-4), which is a salt forming compound of Acid Red 52 and Resin 1 having a cationic group in a side chain, was obtained. At this time, C.I. in the coloring agent (Ad_4) was used. I. The content of the effective dye component derived from Acid Red 52 was 25% by mass.

(Colorant (Ad-5))
C. I. Acid Red 52 is C.I. I. Acid Red 289, except that it was changed to Acid Red 289. I. A colorant (Ad_5), which is a salt forming compound of Acid Red 289 and Resin 1 having a cationic group in a side chain, was obtained. At this time, C.I. in the coloring agent (Ad_5) was used. I. The content of the effective dye component derived from Acid Red 289 was 27% by mass.

(Colorant (Ad-6))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 5.0 parts of basic violet 10 (BV10: Rodamine B, manufactured by Taoka Chemical Co., Ltd.) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1- (3-dimethylaminopropyl) -3-ethyl is dissolved. 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added, and the mixture was stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified by a silica gel column to obtain a colorant (Ad-6).

(Coloring agent (Ad-7))
C. I. Pigment Yellow 138 (“PARIOTOR YELLOW K0961HD”, manufactured by BASF), 100 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 4 hours. The mixture was poured into 3,000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then stirred at 80 ° C. for 24 hours. After drying, a colorant (Ad-7) was obtained.

(Coloring agent (Ad-8))
A coloring agent (Ad-8) represented by the following chemical formula (11) was obtained by a production method similar to that of the yellow coloring agent 8 (Y-8) described in the example of Japanese Patent No. 4993026.

Chemical formula (11)

(Colorant (Ad-9)
According to the synthesis method described in JP-A-2012-226110, a compound represented by the following chemical formula (12) was obtained. 40 parts of the chemical formula (12) and 22 parts of N-bromosuccinimide were added to 300 parts of N, N-dimethylformamide, and the mixture was stirred at 80 ° C for an hour. The reaction solution was poured into a stirred mixed solvent of 300 parts of methanol / 700 parts of water, and stirred at room temperature for 1 hour. The resulting precipitate was treated in the order of filtration, washing with water, washing with methanol, and washing with water, and dried to obtain 48 parts of an intermediate (a-1). 45 parts of the obtained intermediate (a-1), 37 parts of tetrachlorophthalic anhydride and 35 parts of benzoic acid were added to 100 parts of methyl benzoate, and the mixture was heated and stirred at 160 ° C. for 4 hours. After cooling to room temperature, the reaction mixture was poured into 1000 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 65 parts of a quinophthalone compound. A quinophthalone compound (100 parts), sodium chloride (1200 parts), and diethylene glycol (120 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded material was poured into warm water, and stirred for 1 hour while heating to about 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours. A coloring agent (Ad-9) represented by the following chemical formula (13) was obtained.

Chemical formula (12)

Chemical formula (13)

(Colorant (A-d_10))
To 1200 parts of 98% sulfuric acid, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 230 parts of trichloroisocyanuric acid were added and reacted at 80 ° C. for 4 hours. The reaction solution was poured into 9000 parts of stirred ice water, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, washed with water in this order, and dried to obtain an intermediate (a-2). 220 parts were obtained. 105 parts of the compound represented by the chemical formula (12), 150 parts of the intermediate (a-2), and 100 parts of benzoic acid were added, and the mixture was heated to 180 ° C and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5000 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 183 parts of a quinophthalone compound. A quinophthalone compound (100 parts), sodium chloride (1200 parts), and diethylene glycol (120 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded material was poured into warm water, and stirred for 1 hour while heating to about 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours. A coloring agent (Ad-10) represented by the following chemical formula (14) was obtained.

Chemical formula (14)

(Colorant (Ad-11))
Intermediate (a-3) was obtained in the same manner as in the synthesis of intermediate (a-2) except that 350 parts of trichloroisocyanuric acid was changed to 244 parts of N-bromosuccinimide. The number of bromine substituents on the intermediate (a-3) was calculated to be 1.5 on average.
To 200 parts of methyl benzoate, 50 parts of 8-aminoquinaldine, 115 parts of the intermediate (a-2), and 140 parts of benzoic acid were added, and the mixture was stirred at 120 ° C for 4 hours. Next, 143 parts of the intermediate (a-3) was further added to the reaction mixture, and the mixture was heated to 180 ° C and stirred for 4 hours while distilling off water. After cooling to room temperature, the reaction mixture was poured into 2,000 parts of acetone, and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain a quinophthalone compound. A quinophthalone compound (100 parts), sodium chloride (1200 parts), and diethylene glycol (120 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded material was poured into warm water, and stirred for 1 hour while heating to about 70 ° C. to form a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours. A coloring agent (Ad_11) represented by the following chemical formula (15) was obtained.

Chemical formula (15)

(Colorant (A-d_12))
C. I. Pigment Yellow 150 ("Yellow Pigment E4GN" manufactured by LANXESS), 100 parts, sodium chloride (1600 parts) and diethylene glycol (190 parts) were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. Next, the mixture was poured into 3 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and the solvent. It was dried at ℃ for one day and night to obtain a colorant (Ad-12).

(Colorant (Ad-13))
C. I. Pigment Yellow 139 (“IRGAFOR YELLOW 2R-CF” manufactured by BASF), 100 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. . Next, the mixture was poured into 3 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and the solvent. After drying at ℃ for one day, a colorant (Ad-13) was obtained.

(Coloring agent (Ad-14))
C. I. Pigment Yellow 185 ("Pariotor Yellow D1155", manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C for 8 hours. Next, the kneaded material was poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and dried at 80 ° C. all day and night. And a coloring agent (Ad-14).

<Dye derivative>
The following pigment derivatives were used.

(Derivative 1)

<Production method of resin type dispersant 1>
A reaction vessel equipped with a gas inlet tube, a temperature, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate. Was replaced. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the mixture was reacted for 7 hours while adding a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was added to 90 parts of propylene glycol monomethyl ether acetate. The solid content measurement confirmed that 95% had reacted.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst are added, and the mixture is reacted at 100 ° C. for 7 hours. Was. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the solid content to 50% by solid measurement. Resin type dispersant 1 having a value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

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

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

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

(Binder resin (B-4))
A separable flask equipped with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid were used as a monomer dropping tank. A mixture of 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation) and 40 parts of propylene glycol monomethyl ether acetate was prepared by thoroughly stirring and mixing. As a chain transfer agent dropping tank, a well-stirred mixture of 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate was prepared.
The reaction vessel was charged with 395 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the mixture was heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction tank was stabilized at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was performed over a period of 135 minutes while maintaining the temperature at 90 ° C. 60 minutes after the completion of the dropwise addition, the temperature was raised and the temperature of the reaction vessel was set 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. Then, 70 parts of glycidyl methacrylate, 2,2′-methylenebis (4-methyl-6-t-butylphenol) 0. 4 parts, triethylamine 0. 8 parts were charged and reacted at 110 ° C. for 12 hours. Thereafter, 150 parts of propylene glycol monomethyl ether acetate was added, and the mixture was cooled to room temperature. About 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Propylene glycol monomethyl ether acetate was added so that the content was 20% by weight, to obtain a binder resin (B-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per solid was 2 mgKOH / g.

<Production method of coloring composition>
(Production of coloring composition (MB-1))
The following mixture was stirred and mixed so as to be uniform, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (MB-1) having a nonvolatile component of 20% by mass.
Red colorant (P-2) 10.80 parts Derivative 1 1.20 parts Resin-type dispersant 1 6.00 parts Binder resin (B-1) 25.00 parts Propylene glycol monomethyl ether acetate 57.00 parts

(Production of coloring composition (MB-2 to 14, 18 to 25))
Hereinafter, colored compositions (MB-2 to 14, 18 to 25) were prepared in the same manner as the colored composition (MB-1) except that the composition was changed to the composition shown in Table 5. The blending amount of propylene glycol monomethyl ether acetate was adjusted so that the nonvolatile component was 20% by mass.

(Production of coloring composition (MB-15))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 5.0 μm to prepare a coloring composition (MB-15).
Coloring agent (Ad-4) 20.00 parts Propylene glycol monomethyl ether acetate 80.00 parts

(Production of coloring composition (MB-16, 17))
Hereinafter, colored compositions (MB-16, 17) were prepared in the same manner as the colored composition (MB-15) except that the composition was changed to the composition shown in Table 5. The blending amount of propylene glycol monomethyl ether acetate was adjusted so that the nonvolatile component was 20% by mass.

<Production method of epoxy compound solution>
(Epoxy compound solution (C-1))
A commercially available epoxy compound, "EHPE-3150" manufactured by Daicel Corporation, was prepared using propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 20% by weight to obtain an epoxy compound solution (C-1).

(Epoxy compound solution (C-2 to C-10))
Epoxy compound solutions (C-2 to C-10) were prepared in the same manner as the epoxy compound solution (C-1), except that the types of the epoxy compounds were changed to those shown in Table 6.

<Method for producing photosensitive coloring composition>
The following preparations were performed for the production of the photosensitive composition.

[Binder resin B]
The binder resins (B-1) to (B-4) were mixed in the same amount to obtain a binder resin B.

[Photopolymerizable compound D]
(D-1): trimethylolpropane triacrylate
[Aronix M309 (Toagosei Co., Ltd.)]
(D-2): dipentaerythritol penta and hexaacrylate
[Aronix M402 (Toagosei Co., Ltd.)]
(D-3): polybasic acidic acrylic oligomer
[Aronix M520 (Toagosei Co., Ltd.)]
(D-4): Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (Nippon Kayaku)]
(D-5): A pentaerythritol triacrylate (432 g, 84 g of hexamethylene diisocyanate) was charged into a 5-liter reaction vessel having the following polyfunctional urethane acrylate having a content of 1 liter of polyfunctional urethane acrylate and reacted at 60 ° C. for 8 hours to give (meth) acryloyl A product containing a polyfunctional urethane acrylate (D-5) having a group was obtained, wherein the proportion of the polyfunctional urethane acrylate (D-5) in the product was 70% by mass, and the remainder was other photopolymerization. IR analysis confirmed that there was no isocyanate group in the reaction product.
(D-6): Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(D-7): ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
As described above, (D-1) to (D-7) were mixed in the same amounts, respectively, to obtain a photopolymerizable compound D.

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

[Solvent F]
(F-1): 30 parts of propylene glycol monomethyl ether acetate (F-2): 30 parts of cyclohexanone (F-3): 10 parts of ethyl 3-ethoxypropionate (F-4): 10 parts of propylene glycol monomethyl ether (F -5): 10 parts of cyclohexanol acetate (F-6): 10 parts of dipropylene glycol methyl ether acetate Each of (F-1) to (F-6) was mixed in the above parts by weight to obtain a solvent F. .

[Thermosetting compound G]
3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Alon Oxetane OXT-221 (Toagosei Co., Ltd.)]
Was designated as a thermosetting compound G.

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

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

[Polymerization inhibitor J]
(J-1): 3-methylcatechol (J-2): methylhydroquinone (J-3): tert-butylhydroquinone More than (J-1) to (J-3) were mixed in the same amount, Polymerization inhibitor J.

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

[Antioxidant L]
(L-1): pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (L-2): dioctadecyl 3,3′-thiodipropanoate (L-3): Tris [2,4-di- (tert) -butylphenyl] phosphine (L-4): bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5): p-octyl salicylate Phenyl or more and (L-1) to (L-5) were mixed in the same amount, respectively, to obtain an antioxidant L.

[Leveling agent M]
1 copy of "BYK-330" manufactured by Big Chemie
1 copy of MegaFac F-551 manufactured by DIC Corporation
1 part of "Emulgen 103" manufactured by Kao Corporation was dissolved in 97 parts of propylene glycol monomethyl ether acetate to obtain a leveling agent M.

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

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

[Example 1]
(Production of photosensitive coloring composition (R-1))
Coloring composition (MB-1) 26.25 parts Coloring composition (MB-12) 17.50 parts Binder resin B 12.23 parts Epoxy compound solution (C-1) 0.38 part Photopolymerizable compound D 1. 50 parts Photopolymerization initiator E 1.35 parts Solvent F 38.95 parts Thermosetting compound G 0.10 parts Sensitizer H 0.15 parts Thiol chain transfer agent I 0.10 parts Polymerization inhibitor J 0. 10 parts UV absorber K 0.10 parts Antioxidant L 0.10 parts Leveling agent M 1.00 parts Storage stabilizer N 0.10 parts Silane coupling agent O 0.10 parts

[Examples 2 to 39, Comparative Examples 1 and 2]
(Production of photosensitive coloring composition (R-2-41))
Hereinafter, except that the coloring composition (MB-1), the coloring composition (MB-12), the binder resin B, and the epoxy compound solution (C-1) were changed as shown in Table 7, the photosensitive coloring composition ( In the same manner as in R-1), photosensitive coloring compositions (R-2 to 41) were prepared.
The% in the solid content weight of the epoxy compound (C) solution in Table 7 indicates a ratio of the solid content weight of the epoxy compound (C) based on the solid content weight of the photosensitive coloring composition.

<Evaluation of photosensitive coloring composition>
Each test of the flatness, adhesion and solvent resistance of the film was performed by the following methods. Table 8 shows the test results.

(Formation of filter segment)
A black matrix was patterned on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the photosensitive coloring composition obtained by a spin coater was applied on the substrate, and dried at 70 ° C. for 20 minutes. The coating was irradiated with 150 mJ / cm ² ultraviolet light through a photomask using an ultra-high pressure mercury lamp. Then sprayed with an alkali developing solution consisting of 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of an anionic surfactant ("Perex NBL" manufactured by Kao Corporation) and 99.7% by weight of water. After developing to remove unexposed portions, the substrate was washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form red filter segments.

(Film flatness)
The surface of the obtained red filter segment was observed using an optical microscope, and evaluated on the following three levels.
：: No surface unevenness Δ: Surface unevenness can be confirmed only with a reflection light source ×: Surface unevenness can be confirmed with a reflection and transmission light source

(Adhesion)
After performing the pressure cooker test (PCT) on the red filter segment forming substrate at 120 ° C., 100% RH, 2 atm, and 24 hours, JIS K 5600-5-6: 1999 Paint General Test Method—Part 5: Mechanical Properties of Coating Film-Section 6: Adhesion was evaluated on the following three scales by a method based on adhesion (cross-cut method).
：: The edge of the cut is completely smooth, and there is no peeling at any grid. △: A small peeling of the coating film is observed at the intersection of the cuts. ×: The coating film is partially or completely along the edge of the cut. Peeling is seen

(Solvent resistance)
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained red filter segment with the C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. Further, the substrate on which the red filter segment is formed is immersed in NMP for 30 minutes, washed with water, dried, and then chromaticity using a C light source ([L * (2), a * (2), b * (2)]). ) Was measured, and the color difference ΔEab * was determined by the following formula, and evaluated by the following four grades.
ΔEab * = √ ((L * (2) - L * (1)) 2 + (a * (2) - a * (1)) 2 + (b * (2) - b * (1)) 2)
〇: ΔEab * is less than 3.0
Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

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

Claims (7)

A photosensitive coloring composition for a color filter comprising a colorant (A), a binder resin (B), an epoxy compound (C), a photopolymerizable compound (D), a photopolymerization initiator (E) and a solvent (F). A photosensitive coloring composition for a color filter, wherein the coloring agent (A) contains the following chemical formula (1).
The photosensitive coloring composition for a color filter according to claim 1, further comprising a diketopyrrolopyrrole-based pigment represented by the following general formula (2).
[In the general formula (2), X represents a chlorine atom or a bromine atom, and A and B each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbon atom of 1 12 alkyl group, an optionally substituted phenyl _{^{group, -CF 3, -OR 1, -SR}} 2, -N (R 3) R 4, -COOR 5, -CONH 2, -CONHR 6, —CON (R ⁷ ) R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ , or —SO ₂ N (R ¹⁰ ) R ¹¹ , wherein R ^{1 to} R ¹¹ are each independently a carbon number. It is an alkyl group of 1 to 12, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not simultaneously become hydrogen atoms. Further, X is not A and B is a hydrogen atom, or X is B and A is not a hydrogen atom. ] The diketopyrrolopyrrole-based pigments represented by the general formula (2) are represented by the following general formulas (2-1), (2-2), (2-3), and (2-3). The photosensitive coloring composition for a color filter according to claim 2, comprising one or more pigments selected from the group consisting of 2-4).

[In the general formulas (2-1), (2-2), (2-3) and (2-4), X represents a chlorine atom or a bromine atom. In the general formulas (2-3) and (2-4), R ^{12 to} R ¹⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl which may have a substituent. Group. R ¹³ and R ¹⁴ may combine to form an aromatic ring which may have a substituent.]   The epoxy equivalent of the epoxy compound (C) is 100 to 400 (g / eq: molecular weight per epoxy group = molecular weight / number of epoxy groups), and is an epoxy compound. Photosensitive coloring composition for color filters.   The content of the epoxy compound (C) is 0.1 to 15.0% by weight based on the weight of the solid content of the photosensitive coloring composition for a color filter. Item 2. The photosensitive coloring composition for a color filter according to Item 1.   A color filter, comprising: a substrate; and a filter segment formed from the photosensitive coloring composition for a color filter according to claim 1. A liquid crystal display device comprising the color filter according to claim 6.