JP7318770B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

The present invention provides a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and a photosensitive coloring composition used in the manufacture of color filters used in electronic paper and the like, and using the same It relates to a color filter with formed filter segments.

In a liquid crystal display device, a liquid crystal substance and a pixel are interposed between two polarizing plates, and a voltage is applied to each pixel to change the alignment state of the liquid crystal substance. This is a display device that displays a screen by changing and controlling transmitted light passing through the second polarizing plate.
By providing a color filter between these two polarizing plates, a color display becomes possible, and it has come to be used in televisions, personal computer monitors, and the like. In recent years, there has been a demand for high image quality and low power consumption in color liquid crystal display devices, and there is also a demand for a design that achieves high image quality and low power consumption for color filters.

A color filter consists of a transparent substrate such as a glass plate, which is provided with a grid-shaped light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixing of transmitted light and increasing display contrast. green, blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in fine bands (stripes) of two or more different hues (stripe arrangement), or arranged in a constant vertical and horizontal arrangement. There is one arranged by (delta array). The filter segment and BM are coated with a coloring composition and generally heated and baked at a high temperature of 200°C or higher, preferably 230°C. Furthermore, in a color liquid crystal display device, a transparent electrode for driving liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed thereon. In order to obtain sufficient performance of these transparent electrodes and alignment films, it is necessary to form them at a high temperature of generally 200° C. or higher, preferably 230° C. or higher. For this reason, currently, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a coloring material is mainly used as a method for manufacturing a color filter.

In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, dried to remove the solvent, and then subjected to pattern exposure of one filter color. Then, the unexposed areas are removed in the development step to form a pattern of the first color, and if necessary, a treatment such as heating is applied, and then the same operation is sequentially repeated for all filter colors to manufacture a color filter. can do.

In recent years, color liquid crystal display devices have been widely used in various applications, and there is an increasing demand for higher brightness, higher contrast, and a wider color gamut such as the digital cinema (DCI) standard and the Adobe standard.

In order to increase the color gamut of the color filter, it is necessary to increase the content of the pigment in the coloring composition or increase the film thickness. However, in both the method of increasing the pigment content and the method of increasing the thickness of the film, the bottom of the film was not exposed, and the linearity of the tapered portion was deteriorated. Bad problems occur.
As a solution to such problems, one is the need to increase the sensitivity of the coloring composition for color filters, and the use of photopolymerizable monomers, photopolymerization initiators, and chain transfer agents described in Patent Document 1. Selection or increase may be mentioned. There is also a method of using an extender to rectangularize the pattern shape. (Patent document 2)
On the other hand, there is an increasing demand for a colored composition that does not change the line width even when the development time is changed in terms of the manufacturing process of color filters. Furthermore, chemical resistance to N-methylpyrrolidone (NMP) and the like is required in the alignment film forming process, but it has been difficult to meet the above problems.

JP-A-2002-167404 JP 2015-125235 A

An object of the present invention is to provide a photosensitive coloring composition for a color filter that does not overhang the pattern shape even if the pigment concentration is high, has a small change in line width due to development time, and has good chemical resistance, and the same. An object of the present invention is to provide a color filter formed by

<1> A photosensitive coloring composition for a color filter containing a coloring agent (A), a resin-type dispersant, a binder resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator (D) There is
The coloring agent (A) contains a red pigment and a yellow pigment,
The red pigment is C.I. I. Pigment Red 177 and C.I. I. Pigment Red 269 containing at least one selected from the group consisting of
The yellow pigment is C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 185 containing at least one selected from the group consisting of
The resin-type dispersant has an acid value,
The content of the photopolymerizable monomer (C) is 28% by mass or more with respect to the total solid content of the photosensitive coloring composition, and when a film having a thickness of 3.2 μm is formed, a wavelength of 350 to 400 nm A red photosensitive coloring composition for a color filter having a maximum light transmittance of 1% or less.

<2> The photosensitive coloring composition for a color filter, wherein the acid value of the resin type dispersant is 40 to 150 mgKOH/g.

<3> The photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (D) contains an oxime ester compound (D1).

<4> The photosensitive coloring composition for a color filter, wherein the photopolymerizable monomer (C) contains dipentaerythritol hexa(meth)acrylate.

<5> A color filter comprising a base material and a filter segment formed from the photosensitive coloring composition for a color filter.

According to the present invention, the pattern shape does not overhang even if the pigment concentration is high, the change in line width due to development time is small, and the photosensitive coloring composition for color filters has good chemical resistance, and the same can provide a color filter formed using

The photosensitive coloring composition of the present invention contains a coloring agent (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a photopolymerizable monomer ( The content of C) is 25% by mass or more with respect to the total solid content of the photosensitive coloring composition, and when a film having a thickness of 3.2 μm is formed, the maximum transmittance for light with a wavelength of 350 to 400 nm is 1. % or less.
Each constituent component of the photosensitive coloring composition of the present invention is described below.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented.

<Photosensitive coloring composition for color filter>
<Colorant (A)>
The photosensitive coloring composition of the present invention contains a coloring agent (A). The photosensitive coloring composition of the present invention is particularly effective when it contains a red pigment and a yellow pigment.
Pigments that can be used in the present invention include red pigments such as C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48: 4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, azo pigments described in JP 2014-112527, azo pigments described in JP 2013-161026, or diketopyrrolopyrrole pigments described in JP 2011-523433. but not particularly limited to these.

Among these, C.I. I. Pigment Red 254, C.I. I. Pigment Red 177 is preferred, more preferably C.I. I. Pigment Red 177. Other preferred red pigments to be used in combination include naphthol azo pigments, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, benzimidazolone-based, C.I. I. Diketopyrrolopyrrole pigments other than Pigment Red 254.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and quinophthalone compounds described in JP-A-2012-226110, but are not particularly limited thereto.
Among these, C.I. I. Pigment Yellow 138, 139, 150, 185 and quinophthalone compounds described in JP-A-2012-226110 are preferred, and C.I. I. Pigment Yellow 139 and C.I. I. It is at least one selected from the group consisting of Pigment Yellow 185.

In the present invention, pigments other than red pigments and yellow pigments can be used depending on the desired hue.

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

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 Can be mentioned, JP-A-2008-19383, JP-A-2007-320986, zinc phthalocyanine pigments described in JP-A-2004-70342, JP-A-2004-333817, JP-A-2012-247588 Aluminum phthalocyanine pigments and the like described in publications can be used. Among these, from the viewpoint of brightness and coloring strength, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63.

Blue pigments include, for example, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 80 and the like can be used.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used.
Examples of black pigments include carbon black, aniline black, anthraquinone black pigments, and perylene black pigments, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used.

Inorganic pigments include silicon oxide, zirconia oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt. Metal oxide powders such as green, amber, titanium black, synthetic iron black, titanium oxide and iron tetroxide, metal sulfide powders, and metal powders.

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

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

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

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

Chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

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

<Refinement of pigment>
When the coloring agent used in the photosensitive coloring composition of the present invention is a pigment, it is preferably used in a fine form. The method of refining is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation method can be used. etc., and can be miniaturized. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse in an organic solvent, and if it is larger than 90 nm, it may not be possible to obtain a sufficient contrast ratio. For these reasons, the average primary particle size is more preferably in the range of 10 to 70 nm.

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

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

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

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

<Dye derivative>
If necessary, a dye derivative can be added to the photosensitive coloring composition used in the present invention.
As the dye derivative used in the present invention, known dye derivatives having an organic dye residue having an acidic group, a basic group, a neutral group, or the like can be used. For example, compounds having an acidic substituent such as a sulfo group, a carboxyl group, and a phosphoric acid group, amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, a phenyl group, and phthalimide Examples thereof include compounds having a neutral substituent such as an alkyl group.

Examples of organic dyes include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, benzo Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo. be done.
Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine As the dye derivative, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, as the anthraquinone dye derivative, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP-A-48- 54128, JP 03-9961, JP 2000-273383, JP 2011-162662 as a dioxazine dye derivative, JP 2007-314785 as a thiazine indigo dye derivative Publications, as triazine dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP-A-2006-291194, JP-A-2006-291194 2008-31281, JP 2012-226110, as a naphthol dye derivative, JP 2012-208329, JP 2014-5439, as an azo dye derivative, JP 2001-172520 Publication, JP 2012-172092, JP 2004-307854 as an acidic substituent, JP 2002-201377 as a basic substituent, JP 2003-171594, JP 2005 -181383, Japanese Patent Laid-Open No. 2005-213404, and other known dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a sexual group is synonymous with a dye derivative.
These dye derivatives can be used singly or in combination of two or more.

More specifically, the following dye derivatives are preferred.

[Diketopyrrolopyrrole Dye Derivative]

[Phthalocyanine dye derivative]

[Anthraquinone dye derivative]

[Quinacridone dye derivative]

[Dioxazine dye derivative]

[Thiazine indigo dye derivative]

[Triazine dye derivative]

[Benzisoindole dye derivative]

[Quinophthalone dye derivative]

[Naphthol dye derivative]

[Azo dye derivative]

In the general formulas (101) to (112), (114) to (128), (130) to (133),
R ₁₀₁ to R ₁₁₇ , R ₁₂₉ , R ₁₃₀ and R ₁₄₁ to R ₁₄₅ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or a an optionally substituted phthalimidoalkyl group, an optionally substituted acyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), (158), or a group represented by (159). m and n each independently represent a positive integer. However, when one molecule has a plurality of substituents, at least one is a substituent other than a hydrogen atom. Moreover, when there is only one substituent in one molecule, it is a substituent other than a hydrogen atom.

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

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

In the general formulas (150) to (155),
X ₁ represents a direct bond, -SO ₂ -, -CO-, -CH ₂ -, -CH ₂ NHCOCH ₂ -, -CONHC ₆ H ₄ CO-, or -CONHC ₆ H ₄ -.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an optionally substituted arylene group, or an optionally substituted heteroaromatic ring, and these groups are —NR ₁₇₀ — , —O—, —SO ₂ They may be mutually linked by a divalent linking group selected from - or CO-.
Y ₃ represents a direct bond, -NR ₁₇₀ - or -O-.
o represents an integer from 0 to 20;
M ₁ is a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom,
represents an iron atom.
_M2 represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i represents the valence of _M2 .
R ₁₅₀ and R ₁₅₁ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₅₀ and R ₁₅₁ Taken together, it represents a heterocyclic ring which may have further substituents containing nitrogen, oxygen or sulfur atoms.
R ₁₅₂ to R ₁₅₆ and R ₁₅₉ to R ₁₆₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O—(CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — represents Cl, —F or Y ₃ —Y ₂ —Y ₁ —Q, and either one of R ₁₅₇ and R ₁₅₈ is a group represented by the following general formula (156) or (157), —O—(CH ₂ ) _o -R ₁₇₁ , -OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ ;
R ₁₇₀ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
R ₁₇₁ represents a heterocyclic residue which may have a substituent, R ₁₇₂ to R ₁₇₄ each independently
represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group, and Q represents an organic dye residue.

In general formula (156), Z ₁ represents a direct bond, —NR ₁₇₀ —, —CONH— or —O—, Z ₂ is an optionally substituted alkylene group, optionally substituted represents an alkenylene group which may be substituted, an arylene group which may have a substituent, and these groups are mutually bonded through a divalent linking group selected from —NR ₁₇₀ —, —O—, —SO ₂ — and CO—; may have been However, _R170
has the same meaning as R ₁₇₀ in general formulas (150) to (155).
R ₁₅₀ and R ₁₅₁ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₅₀ and R ₁₅₁ together represents a heterocyclic ring which may have a further substituent containing a nitrogen, oxygen or sulfur atom.

In general formula (157), Z ₃ is a single bond connecting the triazine ring and the 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-, -OZ ₄ -CONR ₁₇₅ -, -O-Z ₄ -SO ₂ -, or O-Z ₄ -SO ₂ represents NR ₁₇₅ —, and R ₁₇₅ and R ₁₇₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents a phenyl group, 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.
R ₁₅₂ to R ₁₅₆ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or polyoxyalkylene represents a group.

In general formula (159), X ₂ is —SO ₂ —, —CO—, —NH—, —SO ₂ NH—, —N
HSO ₂ -, -CONH- or -NHCO-, wherein R ₁₆₃ to R ₁₆₇ each independently
A hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, or groups represented by general formulas (150) to (155).

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

By adding a dye derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, or beads, the dye derivative is adsorbed on the surface of the pigment, and the surface of the pigment becomes polar and adsorbs the resin-type dispersant. is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity stability over time when used as a colored composition or colored curable composition are improved. do. In addition, by improving the compatibility, the coating film has excellent temporal stability when the colored curable composition is applied to a glass substrate or the like, and the waiting time from application of the colored curable composition to exposure (PCD: Post
Coating Delay), the waiting time from exposure to heat treatment (PED: Post Exposure Delay), stability and characteristic dependence of pattern shape, and line width sensitivity stability are improved. Further, variations in development time and development residues are suppressed.

<Resin Dispersant>
The photosensitive coloring composition of the present invention contains a resin-type dispersant to stably disperse the pigment.
good too.
The resin-type dispersant has a colorant-affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and adsorbs the added colorant to disperse in the colorant carrier. It works to stabilize the A known resin-type dispersant can be used as the resin-type dispersant.

A preferred example of the resin-type dispersant is a polymer having a hydroxyl group at at least one terminal and

Resin-type dispersants (S1) or (S2) which are reaction products with tricarboxylic anhydrides or tetracarboxylic dianhydrides.
(S1) A resin type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride.
(S2) a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and/or a tetracarboxylic dianhydride; A resin-type dispersant that is a coalesce.

[Resin Dispersant (S1)]
Resin-type dispersant (S1), WO2008/007776, JP 2008-029
901, JP-A-2009-155406, and other known methods. The polymer (p) having a hydroxyl group is preferably a polymer having a terminal hydroxyl group. For example, an ethylenically unsaturated monomer (r) is polymerized in the presence of a compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the terminal has a plurality of hydroxyl groups, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, is obtained by adding a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) by polymerizing the ethylenically unsaturated monomer (r) contained. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of the tricarboxylic anhydride and/or the tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened to form a carboxylic acid. produces

[Resin Dispersant (S2)]
The resin-type dispersant (S2) is disclosed in JP-A-2009-155406 and JP-A-2010-185.
No. 934, JP 2011-157416, etc. can be produced by known methods, for example, the hydroxyl group of the compound (q) having a hydroxyl group, the tricarboxylic acid anhydride and / or the tetracarboxylic acid dianhydride It is obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product with an acid anhydride group. Above all, in the presence of a reaction product between the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and/or tetracarboxylic dianhydride. Furthermore, it is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

(S1) and (S2) are the difference in whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but theoretically the same product can be obtained if the raw materials and reaction conditions are the same.

<Other dispersants>
As a resin-type dispersant other than the above, the following may be contained.

Specifically, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, long Chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and oil dispersants such as salts thereof , (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins and water-soluble high molecular compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphoric acid esters, etc. are used, and these can be used alone or in combination of two or more, but they are not necessarily It is not limited.

In addition to the above, other dispersants include polymer dispersants having basic functional groups, nitrogen atom-containing graft copolymers, tertiary amino groups in side chains, quaternary ammonium bases, nitrogen-containing complex Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including rings may also be included.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240 manufactured by Nippon Lubrizol, 13650,13940,16000,17000,18000,20000,21000,24000,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,3 8500, 41000, 41090, 53095, 55000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF, such as 56000, 76500 , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine-Techno Co., Ltd. Ajisper-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

The resin-type dispersant is preferably used in an amount of about 5 to 200% by mass, more preferably in an amount of about 10 to 100% by mass, based on the total amount of the coloring agent. Furthermore, it is most preferable to be about 10 to 40% by mass in order to achieve good lithography (resolution) in the development process.

Two or more kinds of resin-type dispersants may be contained. In that case, the total amount is preferably within the above range.

The molecular weight Mw of the resin-type dispersant is preferably 5,000 or more and 30,000 or less from the viewpoint of developability. It is more preferably 5,000 or more and 20,000 or less, and most preferably 5,000 or more and 10,000 or less. The acid value is preferably 10 or more and 150 or less, more preferably 40 or more and 120 or less, from the viewpoint of a balance between imparting developability and dispersibility.

<Binder resin (B)>
The photosensitive 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 range of 400 to 700 nm is used. The binder resin (B) can be classified by its main curing method into thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc. Active energy ray-curable resins may be 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 that is not curable with active energy rays, and it is also preferably alkali-soluble. These can be used alone or in combination of two or more.

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

<Alkali-soluble resin>
The photosensitive coloring composition of the present invention preferably contains an alkali-soluble resin in terms of developability, heat resistance and transparency. It is for imparting development solubility in the alkali development process during color filter production, and has an acid group and/or a hydroxyl group. Moreover, in order to further improve the photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond. From the viewpoint of developability, the content of the alkali-soluble resin is preferably 3 parts by mass or more, preferably 5 parts by mass or more based on 100 parts by mass of the solid content of the photosensitive coloring composition.

<Alkali-soluble resin having an ethylenically unsaturated double bond>
The alkali-soluble resin contained in the photosensitive coloring composition of the 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 method (i) or (ii) shown below, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This increases the crosslink density and improves chemical resistance.

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

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

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

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

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

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

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

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like. However, without being limited to these, two or more kinds can be used together.

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

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4′-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-
maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-tri chlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N - succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, etc. N-substituted maleimides of
Compounds represented by the following general formula (8), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenolic ethylene oxide (EO)-modified (meth)acrylate , EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, and PO-modified (meth)acrylates of nonylphenol.

（一般式（８）中、Ｒ₆は、水素原子、又はメチル基であり、Ｒ₇は、炭素数２若しくは３のアルキレン基であり、Ｒ₈は、ベンゼン環を有していてもよい炭素数１～２０のアルキ
ル基であり、ｎは、１～１５の整数である。） general formula (8)

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

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

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

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

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The red 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. Synthesized using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and by not imparting an ethylenically unsaturated bond to the side chain, ethylene Alkali-soluble resins having no polyunsaturated double bonds can be obtained.

The weight-average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, in order to impart alkali developing solubility, and 4,000 More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, the adhesiveness to the substrate is lowered and the exposed pattern is less likely to remain. If it exceeds 40,000, the solubility in alkali development will be lowered, and a residue will be generated to deteriorate the linearity of the pattern.
The acid value of the alkali-soluble resin in the present invention is 30 or more and 200 or less (KOHmg/g) in order to impart alkali developing solubility, preferably in the range of 40 or more and 180 or less.
It is more preferably in the range of 50 or more and 170 or less. If the acid value is less than 30, the solubility in alkali development is lowered, and residues are generated, which deteriorates the linearity of the pattern. If it exceeds 200, the adhesion to the substrate will be lowered, and the exposure pattern will be difficult to remain.

The content of the binder resin (B) in the photosensitive coloring composition of the present invention is preferably 5 to 400 parts by mass, more preferably 10 to 250 parts by mass, based on the total weight of the colorant (100 parts by mass). is. It is preferably used in an amount of 5 parts by mass or more because of good film formability and resistance, and is preferably used in an amount of 400 parts by mass or less because the concentration of the coloring agent is high and good color characteristics can be expressed. .

<Photopolymerizable monomer (C)>
The red photosensitive coloring composition of the present invention contains a photopolymerizable monomer (C), the photopolymerizable monomer (C
) is 25% by mass or more relative to the total solid content of the photosensitive coloring composition.
In the composition of the present invention, the content of the photopolymerizable monomer (C) is within the above-specified range, and when a film having a thickness of 3.2 μm is formed, the maximum transmittance for light with a wavelength of 350 to 400 nm is At 1% or less, the coating film surface hardens, but excessive curing does not occur at the substrate interface, the pattern shape does not overhang even if the pigment concentration is high, and the change in line width due to development time is small. Furthermore, it exhibits the effect of being excellent in chemical resistance. The photopolymerizable monomer (C) includes monomers or oligomers that are cured by ultraviolet light, heat, or the like to form a transparent resin.

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

These commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARADMAND, and KAY manufactured by Nippon Kayaku Co., Ltd.
ARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARAD R-604, KA
YARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA
, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPH
A-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD
DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and Aronix M-303, M-3 manufactured by Toagosei Co., Ltd.
05, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, Viscoat #335HP, Viscoat #700, Viscoat manufactured by Osaka Organic Co., Ltd. #295, Viscoat #330, Viscoat #360, Viscoat #GPT, Viscoat #400, Viscoat #405, Shin-Nakamura Chemical Co., Ltd. NK Ester A-9300 and the like can be preferably used.

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

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

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

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

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

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

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the resistance of the coating increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

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

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

The photopolymerizable monomer (C) of the present invention is preferably a polyfunctional (meth)acrylate, more preferably trimethylolpropatri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, diglycerin EO-modified (meth) acrylate, or polybasic acid-modified (meth) acrylic oligomer, more preferably trimethylolpropane tri (meth) acrylate, di It is at least one selected from the group consisting of pentaerythritol hexa(meth)acrylate and polybasic acid-modified (meth)acrylic oligomer, and particularly preferably dipentaerythritol hexa(meth)acrylate.
Examples of polybasic acid-modified (meth)acrylic oligomers include Aronix series M-305, M-510, M-520, etc., which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The content of the photopolymerizable monomer (C) is 25% by mass or more with respect to the total solid content of the photosensitive coloring composition, and from the viewpoint of line width variability and cross-sectional shape with respect to development time, preferably 28 % by mass or more. In addition, the content of the photopolymerizable monomer (C) is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably the total solid content of the photosensitive coloring composition. It is 34% by mass or less.

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

As the photopolymerization initiator (D), 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)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl -4'-methyldiphenyl sulfide or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4 ,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl) -s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2 ,4-trichloromethyl-(4′-methoxystyryl)-6-triazine and other triazine compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] , or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime ester compounds; bis(2,4 phosphine compounds such as ,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds.
These photopolymerization initiators can be used singly or as a mixture of two or more at an arbitrary ratio as required.

Commercially available acetophenone compounds include "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and "IRGACURE 369" all manufactured by BASF. "(2-(dimethylamino)-2
-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl)-butan-1-one and phosphine compounds are all manufactured by BASF, "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), "IRGACURE TPO" ”(2,4,6-
trimethylbenzoyldiphenylphosphine oxide), and the like.

(Oxime ester compound (D1))
Among these, the photosensitive coloring composition of the present invention preferably contains an oxime ester compound (D1). In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, oxime ester compounds are preferably used because they have high quantum efficiency. be.

Commercially available oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanone, 1-[9 -Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE 02) (both manufactured by BASF), Adeka Optomer N-1919, Adeka Arcles NCI-831 (all manufactured by ADEKA), TRONLYTR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Tenryu New Materials Co., Ltd.) and the like are commercially available. In addition, compounds represented by formulas 2 and 3, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, It is also possible to use an oxime ester-based photopolymerization initiator described in JP-A-2011-020998.

The content of the photopolymerization initiator (D) is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the photosensitive coloring composition, and from the viewpoint of photocurability and developability 0.003 to 7 Parts by mass are more preferred.

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

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives can be mentioned as sensitizers capable of particularly suitable sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
These sensitizers can be used singly or as a mixture of two or more at any ratio as required.
Commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F"(4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.). be done.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

The content when using a sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D) contained in the photosensitive coloring composition, photocuring, developing It is more preferably 5 to 50 parts by mass from the viewpoint of sexuality.

<Solvent>
The photosensitive coloring composition of the present invention is colored by dispersing and penetrating a coloring agent sufficiently in a coloring agent carrier, and applying the composition on a substrate such as a glass substrate so that the dry film thickness becomes 0.2 to 5 μm. Solvents can be included to facilitate film formation. The solvent is selected in consideration of good applicability of the photosensitive coloring composition, solubility of each component of the photosensitive coloring composition, and safety.

Examples of solvents include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5- trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3- methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Examples include propyl acetate and dibasic acid esters.
These solvents may be used singly or as a mixture of two or more at any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, ethylene glycol monomethyl Acetates such as ether acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate, benzyl alcohol, diacetone alcohol, 1- Alcohols such as methoxy-2-propanol and 3-methoxybutanol, ketones such as cyclohexanone, and ethyl 3-ethoxypropionate are preferably used.

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

<Epoxy compound>
The photosensitive coloring composition of the present invention can contain an epoxy compound. As the epoxy compound to be used, a known compound having an epoxy group can be used without particular limitation.

Epoxy compounds include phenol novolak type epoxy resin, cresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin. resins, bisphenol-A novolak-type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.
Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water spots or heat resistance and chemical resistance.

Specific examples of the phenol novolak type epoxy resin include Epiclon N-740, Epiclon N-770, and Epiclon N-775 manufactured by DIC Corporation, and D.I. E. N438, Nippon Kayaku Co., Ltd. RE-306, Mitsubishi Chemical Co., Ltd. jER152, jER154 and the like.

Specific examples of cresol novolac epoxy resins include Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, and Epiclon N-665-manufactured by DIC Corporation. EXP, Epiclon N-672-EXP, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Co., Ltd., and jERE1032H60 manufactured by Mitsubishi Chemical Corporation. be done.

Specific examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 manufactured by DIC Corporation, TACTIX-556 manufactured by Dow Chemical Co., and the like.

Specific examples of bisphenol-type epoxy resins include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Co., Ltd., and D.I. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. An epoxy resin etc. are mentioned.

Specific examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and jERY manufactured by Mitsubishi Chemical Corporation.
Bixylenol type epoxy resins such as X-4000 and JER YL-6121 can be mentioned.

Specific examples of the bisphenol A novolac type epoxy resin include Epiclon N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Specific examples of naphthalene skeleton-containing epoxy resins include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC Corporation.

Specific examples of alicyclic epoxy resins include Seikiside 2021P, 2081, 2000, Epolead PB3600, PB4700, GT401, EHPE-3150, and Cychromer M100 manufactured by Daicel Corporation.

Specific examples of heterocyclic epoxy resins include TEPIC-L, TEPIC-H and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

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

The content of the epoxy compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, based on 100% by weight of the solid content of the coloring composition. When the content of the epoxy compound is within the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<Oxetane compound>
The photosensitive coloring composition of the present invention can contain an oxetane compound. As the oxetane compound, any known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those having a monofunctional oxetane group, those having a bifunctional oxetane group, and those having a bifunctional or higher oxetane group.

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

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

Examples of oxetane groups having two or more functional groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa(3-ethyl). -3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3- ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl)ether, resin containing oxetane group (eg, oxetane-modified phenolic novolac resin described in Japanese Patent No. 3783462) and polymers obtained by radical polymerization of (meth)acrylic monomers such as OXE-30 described above. Such polymers can be obtained using known polymerization methods.

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

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

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

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

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

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

<Ultraviolet absorber (E)>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (E). A UV absorber is an organic compound having a UV absorbing function. A triazine compound (E1) is preferable as the ultraviolet absorber (E). For example, 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4- dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis The reaction product of (2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl"-6-(2 ,4-dibutoxyphenyl)-1,3-5-triazine and the like.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd., "
TINUVIN 400”, ”TINUVIN 405”, ”TINUVIN 460”,
"TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1
577”, “ADEKA STAB LA-46”, “ADEKA STAB LA-F70” manufactured by ADEKA, and “CYASORB UV-1164” manufactured by Sun Chemical.

Other UV absorbers include benzotriazole-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

Examples of benzotriazole-based organic compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3-tert-butyl -4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H -benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-
3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(
3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy- 5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 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.

More specifically, BASF "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN326"
, "TINUVIN 328", "TINUVIN 329", "TINUVIN 360
”, “TINUVIN 384-2”, “TINUVIN 900”, “TINUVIN
928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, and "RUNA-93" manufactured by Otsuka Chemical.
Benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like.

More specifically, "KEMIISORB 10", "KEMIISOR
B 11", "KEMISORB 11S", "KEMISORB 12", "KEMIS
ORB 111”, “SEESORB 101” manufactured by Shipro Kasei Co., Ltd., “SEESORB 10
7”, and “ADEKA STAB 1413” manufactured by ADEKA.

The content of the ultraviolet absorber (E) is blended so that the maximum transmittance for light with a wavelength of 350 nm to 400 nm is 1% or less. As the content of the ultraviolet absorber is increased, the wavelength from 350 nm to
Although the maximum transmittance to light of 400 nm becomes small, the sensitivity of the coating film is lowered. A plurality of the above ultraviolet absorbers (E) may be mixed and used.

<Polymerization inhibitor>
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent exposure due to diffracted light from a mask during exposure. By adding a polymerization inhibitor, it is possible to obtain the effect of preventing curing from progressing outside the desired pattern due to chain polymerization due to photosensitivity.

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

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

The "antioxidant" in the present invention may be a compound having a function of scavenging radicals or a function of decomposing a peroxide. Examples include sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and antioxidants and the like can be used. Moreover, the antioxidant used in the present invention preferably does not contain a halogen atom.

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

Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di -t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4- nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2' thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 2,2′-methylene-bis-(6-(1-methyl -cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide) and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

Specific examples include Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO80, and AO320 manufactured by ADEKA Corporation, KEMINOX101, 179, 76, 9425 manufactured by Chemipro Co., Ltd., 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3, 4-butane tetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4 -diyl) {(2,2,6,6-tetramethyl-4-piperidyl)imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.
Specific examples include ADEKA Corporation ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF Corporation, TINUVIN111FDL, 123, 144, 292, 5100, Cyasorb UV-3346 manufactured by Sun Chemical Co., Ltd., UV -3529, UV-3853 and the like.

Phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl phosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4' isopropylidenediphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2, 4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Specific examples include Adekastab PEP-36, PEP-8, HP-10 manufactured by ADEKA Corporation, Adekastab 2112, 1178, 1500, C, 3013, TPP, IRGAFOS168 manufactured by BASF Corporation, HostanoxP-EPQ manufactured by Clariant Chemicals Co., Ltd., etc. are mentioned.

Sulfur antioxidants include 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, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3- (dodecylthio)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, an oligomer-type or polymer-type compound having a benzotriazole structure can be used.
Specific examples include Adekastab LA-29, LA-31RG, LA-32, LA-36, and -412S manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Kasei Co., Ltd., and TINUVIN PS manufactured by BASF Corporation. , 99-2, 384-2, 900, 928, 1130 and the like.

Benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -methoxy-5-sulfobenzophenone, 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.
Specific examples include Adekastab 1413 manufactured by ADEKA Corporation, KEMIISORB 10, 11, 11S, 12 and 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 and UV-329 manufactured by Sun Chemical Co., Ltd., and the like.

Triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Specific examples include Adekastab LA-46 and F70 manufactured by ADEKA Corporation, KEMIISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479 manufactured by BASF Corporation, and Cyasorb UV-1164 manufactured by Sun Chemical Co., Ltd. .

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

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

Further, the content of the antioxidant is more preferably 0.1 to 5.0% by mass based on 100% by mass of the solid content of the photosensitive coloring composition, because the transmittance, spectral characteristics, and sensitivity are good.

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

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

<Leveling agent>
A leveling agent is preferably added to the photosensitive coloring composition of the present invention for the purpose of improving the coating properties of the composition on a transparent substrate and the drying properties of the colored film. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants and anionic surfactants can be used.
Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Specific examples include BYK-300, BYK-306, BYK-310, BYK-313, BYK-315N, BYK-320, BYK-322, BYK-323, BYK-330, BYK-331, BYK- 333, BYK-342, BYK-345/346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-377, BYK-378, BYK-3455, BYK-UV3510, BYK-3570, Toray Dow Corning Co., Ltd., FZ-7001, FZ-7002, FZ-2110, FZ-2122, FZ-2123], FZ-2191, FZ-5609, Shin-Etsu Chemical Co., Ltd. X-22-4952, X-22 -4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004 etc.

Fluorosurfactants include (surfactant or leveling) agents having fluorocarbon chains.
Specific examples include AGC Seimi Chemical Co., Ltd. Surflon S-242, S-243, S-420, S-611, S-651, S-386, DIC Corporation Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS- 21, FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1 and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., Futergent 602A manufactured by Neos Co., Ltd., and the like.

Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl Ether, Polyoxyalkylene Alkyl Ether, Polyoxyphenylene Distyrenated Phenyl Ether, Polyoxyethylene Tribenzylphenyl Ether, Polyoxyethylene Polyoxypropylene Glycol, Polyoxyethylene Alkenyl Ether, Polyoxyethylene Nonylphenyl Ether, Polyoxyethylene Alkyl Ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan esquioleate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene orbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, tetra Polyoxyethylene sorbitol oleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol mooleate, polyoxyethylene hydrogenated castor oil, polyoxy Examples thereof include ethylene alkylamines, alkylalkanolamides, alkylbetaines such as alkylimidazolines and alkyldimethylaminoacetic acid betaine.

Specific examples include Emulgen 103, Emulgen 104P, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 130K, Emulgen 147, Emulgen 150, Emulgen 210P, Emulgen 220, Emulgen 306P, and Emulgen 320P manufactured by Kao Corporation. , Emalgen 350, Emalgen 404, Emalgen 408, Emargen 409 PV, Emalgen 420, Emalgen 430, Emalgen 705, Emalgen 707, Emalgen 1108, Emulsion 1118S1108, Emargen 11 35S -70, Emalgen 1150S -60, Emalgen 2020G -HA , Emulgen 2025G, Emulgen LS-106, Emulgen LS-110, Emulgen LS-114, Emulgen MS-110, Emulgen A-60, Emulgen A-90, Emulgen B-66, Emulgen PP-290, Latemul PD-420, Latemul PD-430, Latemul PD-430S, Latemul PD450, Rheodor SP-L10, Rheodor SP-P10, Rheodor SP-S10V, Rheodor SP-S20, Rheodor SP-S30V, Rheodor SP-O10V, Rheodor SP-O30V, Rheodor Super SP-L1, Rheodol AS-10V, Rheodol AO-10V, Rheodol AO-15V, Rheodol TW-L120, Rheodol TW-L106, Rheodol TW-P120, Rheodol TW-S120V, Rheodol TW-L106V, Rheodol TW-S320V, Rheodol TW-O120V, Rheodor TW-O106V, Rheodor TW-IS399C, Rheodor Super TW-L120, Rheodor 430V, Rheodor 440V, Rheodor 460V, Rheodor MS-50, Rheodor MS-60, Rheodor MO-60, Rheodor MS-165V, Emanon 1112, Emanon 3199V, Emanon 3299V, Emanon 3299RV, Emanon 4110, Emanon CH-25, Emanon CH-40, Emanon CH-60 (K), Amit 102, Amit 105, Amit 105A, Amit 302, Amit 320, Amino PK -02S, Aminone L-02, Homogenol L-95, ADEKA Co., Ltd. Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, Adeka Pluronic (registered Trademark) TR-701, 702, 704, 913R and the like.

Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and cetyltrimethylammonium chloride, and their ethylene oxide adducts.
Specific examples include Acetamine 24 and 26 manufactured by Kao Corporation, Kotamine 24P and 86P Conc, KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and (meth)acrylic acid-based (co)polymer Polyflow No. 1 manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 and the like.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanolamine lauryl sulfate. , triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.
Specific examples include Futergent 100 and 150 manufactured by Neos Co., Ltd., Adeka Hope YES-25 manufactured by ADEKA Corporation, Adekacol TS-230E, PS-440E, EC-8600, and the like.

When a surfactant is contained in the photosensitive coloring composition of the present invention, the amount of surfactant added is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive coloring composition of the present invention. is preferred, and more preferably 0.005 to 1.0% by mass. Within this range, the applicability of the photosensitive coloring composition, the pattern adhesion, and the transmittance are well balanced. The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types of surfactants. When two or more types are included, the total amount is preferably within the above range.

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

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developing or alkali-developing coloring composition. The solvent-developable or alkali-developable colored composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and additives. etc. 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.

<Dispersing aid>
When the colorant is dispersed in the colorant carrier, a dispersing aid such as a pigment derivative, a dispersant, or a surfactant may be contained as appropriate. Since the dispersing aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has excellent brightness, contrast, and storage stability. becomes better. The dye derivative and dispersant are as described above.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; Although they can be mixed and used, they are not necessarily limited to these.

When a surfactant is added, it 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 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the excess dispersant may affect dispersion. .

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

<Transmittance of coating film>
The photosensitive coloring composition of the present invention has a maximum transmittance of 1% or less for light with a wavelength of 350 to 400 nm when a film having a thickness of 3.2 μm is formed so that the pattern cross-sectional shape at the time of pattern formation is good. It will be. As a method for forming a coating film, the coating film is uniformly coated on a glass substrate by spin coating or the like, then dried, and the obtained coating film is exposed with a high-pressure mercury lamp or the like, and a solvent, an alkaline developer, or the like is used until the unexposed portion is removed. Develop with At this time, the exposure is performed at an exposure amount (saturation exposure amount) or more at which the film thickness after development does not change even if the exposure amount is increased further. The obtained coating film after development is heated and baked at 230° C. for 60 minutes. The transmittance of the coating film thus obtained is measured using a UV-visible spectrophotometer. When the maximum transmittance for light with a wavelength of 350 to 400 nm is 1% or more, the curing reaction of the coating film sufficiently progresses to the inside of the coating film during exposure, so the pattern shape after heating and baking after development becomes an overhang shape. There is The transmittance can be adjusted by adjusting the blending amount of the coloring agent and the ultraviolet absorber.

<Color filter>
Next, the color filter of the present invention will be explained.
The color filter of the present invention comprises a red filter segment, a green filter segment and a blue filter segment. Also, the color filter may further comprise a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment. Among them, at least one color is composed of the photosensitive coloring composition of the present invention.

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

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

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

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

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

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

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

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited by these. In the examples, "parts" and "%" represent "mass parts" and "mass%", respectively. "PGMAC" means propylene glycol monomethyl ether acetate. First, the method for measuring the weight average molecular weight (Mw) of the resin and the acid value of the resin will be described.

<Resin weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the resin is measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, using TSK-GELSUPERHZM-N as a column by connecting two columns, and using THF as a solvent. molecular weight.

<Acid value of resin>
The acid value of the resin is measured according to the potentiometric titration method of JISK0070 (mgKOH
/g) in terms of solid content.

<Method for producing resin-type dispersant>
(Resin type dispersant solution 1)
90 parts of methyl methacrylate, 60 parts of ethyl acrylate, 40 parts of t-butyl acrylate, and 10 parts of methacrylic acid are placed in a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer as the first-stage synthesis. , and 40 parts of propylene glycol monomethyl ether acetate were charged, and purged with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 parts of 2,2'-azobisisobutyronitrile was divided into 20 times and 30 It was added every minute, reacted for 12 hours at 80° C., and it was confirmed by measuring the solid content that 95% had reacted. Next, as a second stage synthesis, 18 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst. was added and reacted at 120° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Thus, a resin type dispersant solution having an acid value per solid content of 42 mgKOH/g and a weight average molecular weight of 9,800 was obtained.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate is added so that the non-volatile content becomes 40% by mass. was obtained.

<Method for Producing Micronized Pigment>
(Red fine-grained pigment (PR-1))
C. I. Pigment Red 177 (PR177) ("Chromophthal Red A2B" manufactured by BASF) 100 parts, 10 parts of pigment derivative (PD-1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol are mixed in a 1 gallon kneader made of stainless steel (Inoue manufactured by Seisakusho) and kneaded at 70°C for 8 hours. This mixture is poured into 2000 parts of warm water, heated to about 80°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80°C for 24 hours. After drying, a red finely divided pigment (PR-1) was obtained.

(Red fine-grained pigment (PR-2))
C. I. Pigment Red 177 (PR177) (“Chromophthal Red A2B” manufactured by BASF) was added to C.I. I. Pigment Red 254 (PR254) ("Irgafore Red B-CF" manufactured by BASF), except that the dye derivative (PD-1-1) was changed to the dye derivative (PD-2-1), red fine processing A red finely divided pigment (PR-2) was obtained in the same manner as in the production of the pigment (PR-1).

(Red finely divided pigment (PR-3))
C. I. Pigment Red 177 (PR177) ("Chromophthal Red A2B" manufactured by BASF) was added to C.I. I. Pigment Red 269 (PR269) ("Toner Magenta F8B" manufactured by Clariant), except that the dye derivative (PD-1-1) was changed to the dye derivative (PD-3-1), the red finely processed pigment (PR -1) to obtain a red finely divided pigment (PR-3).

(Yellow refined pigment (PY-1))
C. I. Pigment Red 177 (PR177) (“Chromophthal Red A2B” manufactured by BASF) was added to C.I. I. Pigment Yellow 139 (PY139) (manufactured by BASF "Irgafor Yellow 2R-CF"), except for changing the dye derivative (PD-1-1) to the dye derivative (PD-3-1), red fine processing A yellow finely divided pigment (PY-1) was obtained in the same manner as in the production of the pigment (PR-1).

(Yellow refined pigment (PY-2))
C. I. Pigment Red 177 (PR177) ("Chromophthal Red A2B" manufactured by BASF) was added to C.I. I. Pigment Yellow 185 (PY185) ("Pariogen Yellow D1155" manufactured by BASF), except for changing the dye derivative (PD-1-1) to the dye derivative (PD-4-1), red finely processed pigment ( A yellow finely divided pigment (PY-2) was obtained in the same manner as in PR-1).

(Yellow refined pigment (PY-3))
C. I. Pigment Red 177 (PR177) (“Chromophthal Red A2B” manufactured by BASF) was added to C.I. I. Pigment Yellow 150 (PY150) ("E4GN" manufactured by Lanxess Co., Ltd.), except that the dye derivative (PD-1-1) was changed to the dye derivative (PD-4-1), red finely processed pigment (PR -1) to obtain a yellow finely divided pigment (PY-3).

<Method for producing pigment dispersion>
(Pigment Dispersion (DR-1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 5 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a red pigment dispersion (DR-1).
Red fine-grained pigment (PR-1): 11.9 parts Dye derivative (PD-1-2): 1.1 parts Dye derivative (PD-1-3): 1.0 parts Resin type dispersant solution 1: 15.0 copies PGMAC: 71.0 copies

(Pigment dispersion (DR-2 to 3, DY-1 to 3))
Hereinafter, the same as the photosensitive red colored composition (R-1) except that the finely divided pigment, the dye derivative, the acidic resin-type dispersant solution, and the solvent are changed to the types and blending amounts (parts by mass) shown in Table 1. Thus, photosensitive red and yellow colored compositions (DR-2 to 3, DY-1 to 3) were prepared.

The dye derivatives in Table 1 are shown in Table 2.

<Method for producing binder resin solution>
(Binder resin solution (B-1))
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device was charged with 196 parts of methoxypropyl acetate, the temperature was raised to 80° C., the inside of the reaction vessel was replaced with nitrogen, and the dropping tube was added. From, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. "Aronix M110") 20.7 parts , 2,2'-azobisisobutyronitrile 1.1 parts was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. was added to prepare a binder resin solution (B-1). The weight average molecular weight (Mw) was 26,000.

(Binder resin solution (B-2))
A separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of methoxypropyl acetate. , paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2 .0 part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120°C for 3.5 hours to produce an acrylic resin having a weight average molecular weight (Mw) of 19,000. A solution was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180° C. for 20 minutes to measure the nonvolatile content. An acrylic resin solution (B-2), which is an active energy ray-curable resin, was prepared by addition.

ＰＧＭＡＣ ：３２．１８部 <Method for producing photosensitive coloring composition for color filter>
[Example 1]
(Photosensitive red composition (RR-1))
The following mixture was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a photosensitive red composition (RR-1).
Pigment dispersion (DR-1): 44.23 parts Pigment dispersion (DY-1): 11.06 parts Binder resin solution (B-1): 3.50 parts Binder resin solution (B-2): 3. 50 parts Photopolymerizable monomer (C-1): 5.40 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (D-1) represented by the following structure: 0.14 parts

PGMAC: 32.18 copies

[Examples 2 to 17, Comparative Examples 1 to 4]
(Photosensitive red composition (RR-2 to 21)
Below, the pigment dispersion, the binder resin solution, the photopolymerizable monomer, the photopolymerization initiator, the ultraviolet absorber, and the solvent were changed to the types and amounts (parts by mass) shown in Tables 3 and 4. Photosensitive red compositions (RR-2 to 21) were prepared in the same manner as the red composition (RR-1).

<Evaluation of photosensitive coloring composition for color filter>
Transmittance, line width variability with respect to development time, and cross-sectional shape of the photosensitive colored compositions obtained in Examples and Comparative Examples were evaluated by the following methods. Results are shown in Tables 3 and 4.

<Transmittance>
The resulting photosensitive red composition was applied onto a glass substrate of 100 mm×100 mm and 0.7 mm thickness using a spin coater at a rotation speed of 3.2 μm after heating and baking. After drying under reduced pressure, ultraviolet exposure was performed using a high-pressure mercury lamp at an integrated light amount of 50 mJ and an illuminance of 20 mW. After that, using a 0.2% by mass sodium carbonate aqueous solution as a developer, development was carried out for a development time of 40 seconds. After that, it was heated and baked at 230° C. for 60 minutes to prepare an evaluation substrate 1 . Using the obtained evaluation substrate 1, transmittance was measured. The transmittance was measured using a spectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science). The spectroscopy of the obtained resist was evaluated by the maximum transmittance from 350 nm to 400 nm measured from 300 nm to 500 nm in steps of 1 nm.

<Line width variability with respect to development time>
The resulting photosensitive red composition was applied onto a glass substrate of 100 mm×100 mm and 0.7 mm thickness using a spin coater at a rotation speed such that the film thickness after heating and baking was 3.2 μm.
After drying under reduced pressure, it was exposed to ultraviolet light at an integrated light amount of 50 mJ and an illuminance of 20 mW through a photomask including a 100 μm stripe pattern and a 50 μm fine line pattern using an ultra-high pressure mercury lamp. After that, using a 0.2% by mass sodium carbonate aqueous solution as a developer, development was carried out for 10 seconds after the unexposed portions of the coating film were removed by development, and a pattern was formed. After that, the evaluation substrate 2 was prepared by heating and baking at 230° C. for 60 minutes.
An evaluation substrate 3 was prepared in the same manner as the evaluation substrate 2 except that the development time was further changed to 40 seconds after the unexposed portion of the coating film was removed by development.
Regarding the obtained evaluation substrates 2 and 3, the line width of the thin line portion of 50 μm was measured using an optical microscope, and the difference was calculated as the line width variation. The evaluation was evaluated in the following three stages.
◎: Line width variation is less than 2 μm ○: Line width variation is 2 μm or more and less than 6 μm ×: Line width variation is 6 μm or more

<Pattern cross-sectional shape>
Using the evaluation substrate 2, the pattern shape was confirmed with a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, an SEM image of a striped pattern with a width of 100 μm was captured, and the angle of the tapered portion was evaluated using a protractor as follows.
The evaluation was evaluated in the following three stages.
◎: Good taper shape (taper angle less than 70°)
○: Practical taper shape (taper angle of 70° or more and less than 90°)
×: Overhang (taper angle is 90° or more)

<Chemical resistance>
The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the pattern of the 100 μm photomask portion of the filter segment formed by the above method under the C light source was measured with a microscopic spectrophotometer (Olympus). It was measured using “OSP-SP100” manufactured by Kogaku Co., Ltd.). After that, it was immersed in an N-methylpyrrolidone solution for 30 minutes, washed with deionized water, and air-dried. The pattern in the 100 μm photomask portion was observed and evaluated using an optical microscope. The chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) was measured with C light source for the sample without peeling, and the color difference ΔE ^* a ^* b ^* was calculated by the following formula. asked.
ΔE ^* a ^* b ^* ={(L ^* (2)−L ^* (1)) ² +(b ^* (2)−b ^* (1)) ²⁺ (a ^* (2)−a ^* (1) ) ² } ^0.5
Evaluation was made in the following four stages.
◎: No peeling, ΔE ^* a ^* b ^* is less than 1.0 ○: No peeling, ΔE ^* a ^* b ^* is 1.0 or more and less than 3.0 △: No peeling, ΔE ^* a ^* b ^* is 3 .0 or more ×: peeling

Abbreviations in Tables 3 and 4 are described below.
Photopolymerizable monomer (C-1): "Aronix M402" manufactured by Toagosei Co., Ltd., dipentaerythritol penta and hexaacrylate (pentaacrylate content (%): 30-40)
Photopolymerizable monomer (C-2): "Aronix M309" manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate Photopolymerizable monomer (C-3): "Aronix M520" manufactured by Toagosei Co., Ltd., polybasic acid Modified acrylic oligomer photoinitiator (D-2): ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ( BASF "IRGACUREOXE02")
Photopolymerization initiator (D-3): "ADEKA Arkles NCI-831" manufactured by ADEKA
Photopolymerization initiator (D-4): (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (manufactured by BASF "IRGACURE369")
UV absorber (E-1): 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (BASF Japan Ltd.) company “TINUVIN 460”)
UV absorber (E-2): 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (manufactured by BASF Japan Ltd. "TINUVIN 326" )

The content of the photopolymerizable monomer (C) is 25% by mass or more with respect to the total solid content of the photosensitive coloring composition, and when a film having a thickness of 3.2 μm is formed, a wavelength of 350 to 400 nm The photosensitive coloring composition of the present invention having a maximum light transmittance of 1% or less (Examples 1-17) has good line width variability with respect to development time, good cross-sectional shape, and good chemical resistance. Met. On the other hand, Comparative Example 1 had poor line width variability with respect to development time and poor chemical resistance, and Comparative Examples 2 to 4 had poor cross-sectional shape and poor chemical resistance. Above all, when Example 1 is compared with Comparative Examples 1 and 2, it is found that the line width variability with respect to development time and the cross-sectional shape are good, and the chemical resistance is also improved. The reason for this is that by increasing the amount of photopolymerizable monomers, the sensitivity near the surface is increased to suppress changes in color difference, and by lowering the transmittance at 350 to 400 nm, excessive photocuring at the interface with the substrate is suppressed and adhesion is prevented. This is thought to be due to the fact that the

<Production of color filter>
A green photosensitive coloring composition and a blue photosensitive coloring composition for use in preparing color filters were prepared in combination with the photosensitive coloring composition of the present invention.

(Preparation of photosensitive green composition (RG-1))
After stirring and mixing the mixture of the following composition uniformly, using zirconia beads with a diameter of 0.5 mm, an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII
”) for 5 hours and filtered through a 5.0 μm filter to prepare a green composition (DG-1).
Green pigment (CI Pigment Green 58): 12.0 parts Resin type dispersant (manufactured by BASF Japan "EFKA4300"): 1.0 parts Binder resin solution (B-1): 35.0 parts PGMAC: 52 .0 copy

Subsequently, a mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a photosensitive green composition (RG-1).
Green composition (DG-1): 34.0 parts binder resin solution (B-1): 15.2 parts photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M402"): 3.3 parts photopolymerization initiation Agent (BASF Japan "IRGACURE907": 2.0 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd. "EAB-F"): 0.4 parts Ethylene glycol monomethyl ether acetate: 45.1 parts

(Preparation of photosensitive blue composition (RB-1))
After stirring and mixing the mixture of the following composition uniformly, using zirconia beads with a diameter of 0.5 mm, an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII
”) for 5 hours and filtered through a 5.0 μm filter to prepare a blue colored composition (DB-1).
Blue pigment (C.I. Pigment Green 15:6): 12.0 parts Resin type dispersant (manufactured by BASF Japan "EFKA4300"): 1.0 parts Binder resin solution (B-1): 35.0 parts PGMAC : 52.0 copies

Subsequently, a mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a photosensitive blue composition (RB-1).
Blue composition (DB-1): 34.0 parts Binder resin solution (B-1): 15.2 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. "Aronix M402"): 3.3 parts Photopolymerization initiation Agent (BASF Japan "IRGACURE907": 2.0 parts Sensitizer (Hodogaya Chemical Industry Co., Ltd. "EAB-F"): 0.4 parts Ethylene glycol monomethyl ether acetate: 45.1 parts

A black matrix was patterned on a glass substrate, and the photosensitive red composition (RR-1) of the present invention was coated on the substrate by a spin coater so as to have a thickness of 3.2 μm after heat treatment to form a colored film. The film was irradiated with ultraviolet rays of 50 mJ/cm ² using an ultra-high pressure mercury lamp through a photomask. Next, after removing the unexposed portions by spray development with an alkali developer consisting of a 0.2% by mass sodium carbonate aqueous solution, the substrate is washed with deionized water, and the substrate is heat-treated at 230° C. for 20 minutes to obtain a red filter. formed a segment. By the same method, the photosensitive green composition (RG-1) is formed into a green filter segment so that the film thickness becomes 3.2 μm after heat treatment, and then the photosensitive blue composition (RB-1) is formed. A blue filter segment was formed by coating each layer to a film thickness of 3.2 μm after heat treatment, and a color filter was obtained.

It was confirmed that a color filter having an excellent cross-sectional shape can be produced with a high yield without being affected by the development process by using the photosensitive coloring composition for color filters of the present invention.

Claims (4)

A photosensitive coloring composition for a color filter containing a coloring agent (A), a resin type dispersant, a binder resin (B), a photopolymerizable monomer (C), and a photopolymerization initiator (D),
The content of the coloring agent (A) is 37 to 48% by mass with respect to the total solid content of the photosensitive coloring composition,
The coloring agent (A) contains a red pigment and a yellow pigment,
The red pigment is C.I. I. Pigment Red 177 and C.I. I. Pigment Red 269 containing at least one selected from the group consisting of
The yellow pigment is C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150 and C.I. I. Pigment Yellow 185 containing at least one selected from the group consisting of
The resin-type dispersant has an acid value, and the acid value of the resin-type dispersant is 40 to 150 mgKOH/g,
The binder resin (B) contains an alkali-soluble resin,
The content of the photopolymerizable monomer (C) is 28% by mass or more with respect to the total solid content of the photosensitive coloring composition, and when a film having a thickness of 3.2 μm is formed, a wavelength of 350 to 400 nm A red photosensitive coloring composition for a color filter having a maximum light transmittance of 1% or less. The red photosensitive coloring composition for color filters according to claim 1 , wherein the photopolymerization initiator (D) contains an oxime ester compound (D1). 3. The red photosensitive coloring composition for color filters according to claim 1 , wherein the photopolymerizable monomer (C) contains dipentaerythritol hexa(meth)acrylate. A color filter comprising a base material and a filter segment formed from the red photosensitive coloring composition for a color filter according to any one of claims 1 to 3 .