JP7230480B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

The present invention relates to a color liquid crystal display device, a photosensitive coloring composition for color filters used in the manufacture of color filters used in color imaging devices, etc., and a color filter having filter segments formed using the same. It is.

In recent years, color filters are required to have high color reproducibility in order to display darker and more vivid colors. In order to achieve high color reproduction, it is necessary to increase the amount of pigment contained in each of the red, green, and blue color filter pixels. As a method for increasing the pigment content, there is a method of increasing the film thickness of each pixel or a method of increasing the pigment concentration of the photosensitive coloring composition.

In the manufacturing process of the color filter pixel, the coating film of the photosensitive coloring composition is irradiated with ultraviolet rays to cure the coating film, and in order to promote the polymerization of the coating film, the heating process is performed as necessary. including. However, when the amount of pigment in the color filter pixel increases, the ultraviolet rays do not reach the bottom of the coating film, and although the surface is hardened, the bottom of the coating film is not hardened. When the coating film is heated in this state, wrinkles occur on the surface of the coating film due to the difference in heat shrinkage between the surface that has hardened due to ultraviolet irradiation and the bottom that has not hardened.

If wrinkles occur on the surface of the coating film, it is not preferable because color unevenness occurs when colors are displayed with a color filter. In particular, green pixels tend to be wrinkled, and it is necessary to suppress the occurrence of wrinkles by selecting preferable materials for the photosensitive coloring composition. (Patent Documents 1 and 2)

In addition, in the step of removing the ultraviolet-unexposed portion of the coating film of the photosensitive coloring composition with an alkaline developer, if peeled pieces of the coating film float, they cause clogging of pipes. Therefore, the unexposed portion of the coating film is required to have an aptitude (hereinafter referred to as peel developability) in which it is easily dissolved in a developer.

JP 2017-142480 A JP 2017-137483 A

However, the colored resin composition described in Prior Document 1 and the colored resin composition containing a thiol compound described in Prior Document 2 have improved surface properties, but poor peel developability and poor chemical resistance.

That is, the present invention is a photosensitive coloring composition for color filters that does not cause wrinkles on the surface of the coating film and has excellent chemical resistance and peel developability, and the photosensitive coloring composition for color filters. To provide a color filter that is

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that, as a specific photopolymerization chain transfer agent, at least a thiol compound having a carboxyl group is contained to prevent wrinkles in color filter pixels. A photosensitive coloring composition for a color filter that can obtain a color filter that does not generate wrinkles and has excellent chemical resistance, and a color filter that does not generate wrinkles and has excellent chemical resistance. I came up with the invention.

That is, the present invention includes a green pigment (A), a polymerizable compound (B), a thiol compound having a carboxyl group (C), a binder resin (D), and a photopolymerization initiator (E) for a color filter. It relates to a sexual coloring composition.

The photosensitive coloring composition for a color filter, wherein the thiol compound (C) having a carboxyl group is a monofunctional thiol (C-1) having a carboxyl group.

The thiol compound (C) having a carboxyl group relates to the photosensitive coloring composition for color filters, wherein the compound (C-1A) represented by the following general formula (1).
General formula (1)

(In general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms.)

The photosensitive coloring composition for a color filter, wherein the content of the thiol compound (C) having a carboxyl group is 1.0% by mass or more and 10.0% by mass or less with respect to the total solid content of the photosensitive coloring composition. about things.

The present invention relates to the photosensitive coloring composition for color filters, wherein the polymerizable compound (B) is a polyfunctional urethane acrylate.

The present invention relates to a color filter comprising a green filter segment formed from the photosensitive coloring composition for a color filter on a substrate.

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

A photosensitive coloring composition for color filters that does not cause wrinkles in color filter pixels and is excellent in chemical resistance and peel-developability by the photosensitive coloring composition for color filters of the present invention, and the photosensitive coloring composition for color filters It is possible to obtain a high-quality color filter using the colorant composition.

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

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

<Green pigment (A)>
The photosensitive composition of the present invention contains a green pigment (A). Examples of the green pigment (A) include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like, but are not particularly limited to these. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62 or 63.
Further, the photosensitive coloring composition of the present invention may be used in combination with a yellow pigment described later.

<Yellow pigment>
Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231 and the like. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

<Other coloring agents>
The photosensitive composition of the present invention can contain coloring agents such as pigments and dyes other than the green pigment (A) and the yellow pigment.

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

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

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of heat resistance, light resistance and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6. Moreover, you may use the below-mentioned purple pigment together with a blue coloring composition.

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

Cyan-colored compositions for forming cyan-colored filter segments include, for example, C.I. I. Blue pigments such as Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16 and 81 can be used singly or in combination.

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

Inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, and amber. , synthetic iron black, and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good applicability, sensitivity, developability, etc. while balancing chroma and lightness.

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

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

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

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

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

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

<Refinement of pigment>
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, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like in a batch or continuous manner. 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, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. 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, a known dye derivative having an acidic group, a basic group, a neutral group, or the like in the organic dye residue 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, phenyl group, and phthalimide A compound having a neutral substituent such as an alkyl group is included.
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 , R ₁₄₁ to R ₁₄₅ are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group, a substituted a phthalimidoalkyl group which may have a group, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, a halogen group, general formulas (150) to (155), (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, halogen atom, nitro group, cyano group, hydroxyl group, alkoxy group, aryloxy group, —SO ₂ R ₁₇₇ or —NR ₁₇₈ R ₁₇₉ . provided that R ₁₇₇ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, or a halogen atom, and R ₁₇₈ and R ₁₇₉ are each independently a hydrogen atom , an alkyl group having 1 to 12 carbon atoms, or R ₁₇₈ and R ₁₇₉ together represent a heterocyclic ring which may contain an additional nitrogen, oxygen or sulfur atom.
R ₁₁₉ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted acyl group.
R ₁₂₀ , R ₁₂₁ , R ₁₂₃ to R ₁₂₈ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, a halogen atom, a cyano group, a substituent or NR ₁₈₀ R ₁₈₁ . provided that R ₁₈₀ and R ₁₈₁ are each independently a hydrogen atom, an optionally substituted alkyl group, or R ₁₈₀ and R ₁₈₁ together may contain a further nitrogen, oxygen or sulfur atom represents a good heterocycle.
R ₁₂₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted acyl group, or a group represented by general formulas (150) to (155).

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

In the general formulas (150) to (155),
X ₁ represents a direct bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC ₆ H ₄ CO-, or -CONHC ₆ H ₄ -.
Y ₁ represents a direct bond, —NR ₁₇₀ SO ₂ —, —SO ₂ NR ₁₇₀ —, —CONR ₁₇₀ —, —NR ₁₇₀ CO—, or —CH ₂ NR ₁₇₀ COCH ₂ NR ₁₇₀ —.
Y ₂ represents a direct bond, an optionally substituted arylene group, or an optionally substituted heteroaromatic ring, and these groups are —NR ₁₇₀ − , —O—, —SO ₂ They may be mutually linked by a divalent linking group selected from - or CO-.
Y ₃ represents a direct bond, -NR ₁₇₀ - or -O-.
o represents an integer from 0 to 20;
_M1 represents a hydrogen atom, a copper atom, a zinc atom, a manganese atom, a nickel atom, a cobalt atom or an iron atom.
_M2 represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of _M2 .
R ₁₅₀ and R ₁₅₁ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁₅₀ and R ₁₅₁ represents an optionally substituted heterocyclic ring which together contains an additional nitrogen, oxygen or sulfur atom.
R ₁₅₂ to R ₁₅₆ and R ₁₅₉ to R ₁₆₂ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents a phenyl group or a polyoxyalkylene group.
R ₁₅₇ and R ₁₅₈ are each independently a group represented by the following general formula (156) or (157), —O—(CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , —NR ₁₇₃ R ₁₇₄ , — represents Cl, —F or Y ₃ —Y ₂ —Y ₁ —Q, and one of R ₁₅₇ and R ₁₅₈ is a group represented by the following general formula (156) or (157), —O—(CH ₂ ) _o —R ₁₇₁ , —OR ₁₇₂ , or NR ₁₇₃ R ₁₇₄ ;
R ₁₇₀ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
R ₁₇₁ represents a heterocyclic residue which may have a substituent, and R ₁₇₂ to R ₁₇₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, or a represents an alkenyl group or a phenyl group which may have a substituent, and Q represents an organic dye residue.

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

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

In general formula (159), X2 represents -SO2-, -CO-, -NH-, -SO2NH-, -NHSO2-, -CONH- or -NHCO-, and R163 to R167 each independently represent hydrogen It is an atom, an alkoxyl group, an amino group, a sulfo group, a carboxyl group, a phosphoric acid group, or a group represented by general formulas (150) to (155).

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

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

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

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

<Resin Dispersant>
A known resin-type dispersant can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant (M) has a colorant-affinity site having a property of adsorbing to the added colorant and a site compatible with the colorant carrier, and adsorbs the added colorant to the colorant carrier. Specific examples include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids ( Part) Amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and liberation Oil-based dispersants such as amides and salts thereof formed by reaction with a polyester having a carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, Water-soluble resins such as styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used. These can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

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, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000 manufactured by Lubrizol Japan 、１３２４０、１３６５０、１３９４０、１６０００、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２５５０、３３５００、３２６００、３４７５０、３５１００、３６６００、３８５００、４１０００、４１０９０、５３０９５ , 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 manufactured by BASF, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, Ajinomoto Fine-Techno Co., Ltd. Ajisper-PA111, PB711, PB821, PB822, PB824, and the like.

A resin-type dispersant having a carboxyl group can be suitably used in the photosensitive coloring composition of the present invention. As for the shape of the resin-type dispersant having a carboxyl group, there are a straight-chain resin-type dispersant and a comb-shaped resin-type dispersant.

[Comb-shaped resin-type dispersant having carboxyl group]
A comb-shaped resin-type dispersant having a carboxyl group is disclosed in WO2008/007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416. It can be produced by a known method such as
For example, a resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, or a hydroxyl group of a compound having a hydroxyl group and a tetracarboxylic dianhydride It is a resin-type dispersant that is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride group of a compound. Alternatively, in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tetracarboxylic dianhydride, it has a hydroxyl group, a t-butyl group, an oxetane skeleton, a thermal cross-linking group such as a blocked isocyanate. A resin-type dispersant obtained by reacting an ethylenically unsaturated monomer and a resin-type dispersant having a side chain polymerized with other monomers and an ethylenically unsaturated monomer having an isocyanate group in the hydroxyl group of the side chain. is.

[Linear resin-type dispersant having carboxyl group]
A linear resin-type dispersant having a carboxyl group can be produced by known methods such as those disclosed in JP-A-2009-251481, JP-A-2007-23195 and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic acid anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end. can be done.

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

<Binder resin (D)>
The photosensitive coloring composition of the present invention contains a binder resin (D). As the binder resin (D), a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm is used. The binder resin (D) includes thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc., when classified according to their main curing methods. 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 may be used alone or in combination of two or more.

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

<Thermoplastic resin>
Examples of thermoplastic resins that can be used as the binder resin (D) 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 as the binder resin (D) 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. As the alkali-soluble resin, an alkali-soluble resin having no ethylenically unsaturated double bond or an alkali-soluble resin having an ethylenically unsaturated double bond that improves the photosensitivity of the composition can be used alone or in combination. use.

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

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 30,000 or less, and 4,000, in order to impart alkali developing solubility. More than 20,000 or less is more preferable. Also, the value of Mw/Mn is preferably 10 or less. When the weight average molecular weight (Mw) is 2,000 or more, the adhesiveness to the substrate is improved, and an excellent exposure pattern can be obtained. When the weight average molecular weight (Mw) is 40,000 or less, the solubility in alkali development is good, and the pattern linearity is good without residue.

The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) for imparting alkali development solubility, preferably 70 or more and 180 or less, more preferably 90 or more and 170 or less. Range. When the acid value is 50 or more, the solubility in alkali development is improved, and when the acid value is 200 or less, the adhesion to the substrate is excellent.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The photosensitive coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. 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.

<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 it.

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

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

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

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

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

Examples of 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 mono (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, these may be used alone, two or more may be used in combination. 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 preferable from the viewpoint of suppressing coating film foreign matter, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. and more preferably glycerol mono(meth)acrylate.

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

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

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

general formula (2)

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

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

A hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of hydroxyl group-containing ethylenically unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, or cyclohexane. Hydroxyalkyl (meth)acrylates such as dimethanol 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.

<Thermosetting compound (F)>
In the present invention, a thermosetting compound (F) can be further included in combination with the thermoplastic resin that is the binder resin. When producing a color filter using the photosensitive coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts during baking of the filter segment and increases the crosslink density of the coating film, so that the heat resistance of the filter segment As a result, it is possible to obtain the effect of improving the properties, suppressing pigment aggregation during baking of the filter segment, and improving the contrast ratio.

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

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

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

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

(oxetane compound)
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 OXT-212 manufactured by Toagosei Co., Ltd., and the like.

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

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

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

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

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

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

(curing agent)
In addition, the photosensitive coloring composition for color filters of the present invention may contain a curing agent (curing accelerator) and the like, if necessary, in order to assist curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and can react with thermosetting compounds. Any hardener may be used. Curing agents include, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl- 4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino -S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) can be done. These may be used individually by 1 type, and may use 2 or more types together. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting compound.

<Polymerizable compound (B)>
The photosensitive coloring composition of the present invention contains a polymerizable compound (B). The polymerizable compound (B) includes a monomer or oligomer that forms a transparent resin by curing with ultraviolet light, heat, or the like.

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

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

(Polymerizable compound having acid group)
The polymerizable compound (B) in the invention may contain a photopolymerizable compound having an acid group. By using a photopolymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is subjected to alkali development, the solubility of the formed coating film in an alkali developer can be increased, and the development speed can be improved. Residue can be reduced. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Examples of the photopolymerizable compound 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; Examples thereof include esterified products with alkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

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

(Polymerizable compound having urethane bond)
The polymerizable compound (B) in the present invention preferably contains a photopolymerizable compound having at least one ethylenically unsaturated bond and at least one urethane bond. By containing a photopolymerizable compound having a urethane bond, it is possible to suppress deposition of a coloring material when the formed coating film is heated, and to improve solvent resistance and adhesion to a substrate. Polyfunctional urethane acrylate is particularly preferred from the viewpoint of chemical resistance.

As the polymerizable compound having a urethane bond, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional isocyanate obtained by reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group (meth) ) polyfunctional urethane acrylates obtained by reacting acrylates, and the like.

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

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

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

The above polymerizable compound (B) can be used singly or as a mixture of two or more at an arbitrary ratio as necessary.

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

<Photoinitiator (E)>
The photosensitive composition of the present invention contains a photoinitiator (E). By containing the photopolymerization initiator (E), 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 (E) to prepare a solvent-developable or alkali-developable photosensitive composition.

As the photopolymerization initiator (E), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) Phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Acetophenone compounds such as; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2- Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl )-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)- Triazine compounds such as 6-triazine or 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]- ,2-(O-benzoyloxime), or oximes such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ester compounds; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, quinone-based compounds such as ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-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 "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), "Omnirad 379EG" (2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and the phosphine compounds are all "Omnirad 819" (bis(2,4, 6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The optionally substituted arylsulfinyl group for Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group , 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylamino Examples include, but are not limited to, a phenylsulfinyl group.

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

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

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

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

Examples of the amino group which may have a substituent for Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group, and the like. mentioned.

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

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

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

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

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

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

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

The sulfamoyl group which may have a substituent for Y ¹ includes a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group and an N-arylsulfamoyl group. groups, N,N-dialkylsulfamoyl groups, N,N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamoyl groups, and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group. famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylamino phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,N-dimethylsulfamoyl group group, N,N-dibutylsulfamoyl group, N,N-diphenylsulfamoyl group and the like, but are not limited thereto.

an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, which may have a substituent for Y ² ; As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, an alkenyl group which may have a substituent, an alkyl group which may have a substituent, and a substituent for R1 described above are optionally substituted alkyloxy group, optionally substituted aryloxy group, optionally substituted heterocyclic group, optionally substituted heterocyclic oxy group, optionally substituted alkylsulfanyl group, optionally substituted arylsulfanyl group, optionally substituted alkylsulfinyl group, optionally substituted good arylsulfinyl group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group, optionally substituted acyloxy group, and optionally substituted Synonymous with amino group.

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

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

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

General formula (4) corresponds to the case where Y ³ in general formula (3) is a Ph-S-Ph- group, and Y ⁴ to Y ⁶ are hydrogen atoms or optionally substituted alkyl groups, aryl groups, and acyl groups are preferred. The optionally substituted alkyl group or optionally substituted aryl group for Y ⁴ to Y ⁶ is the same as the alkyl group or aryl group for Y ¹ and Y ² .

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

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

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

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

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (4a) include photopolymerization initiators represented by the following chemical formulas (4a-1) and (4a-2).

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

General formula (4b) corresponds to the case where Z in general formula (4) is a direct bond. As the oxime ester photopolymerization initiator represented by the general formula (4b), Y ¹ and Y ² are preferably alkyl groups having 1 to 20 carbon atoms which may have a substituent, and Y ⁴ to Y ⁶ An acyl group, at least one of which may have a substituent, is preferred. Specifically, it is a photopolymerization initiator represented by the following chemical formula (4a-1) or (4a-2).

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

General formula (5) corresponds to the case where Y ³ in general formula (3) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

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

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

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

General formula (5a) corresponds to the case where Z in general formula (5) is a direct bond and Y ³ is a monovalent organic group containing a carbazole group which may have a substituent; Y ⁷ to Y ¹⁰ and Y ¹² to Y ¹³ are hydrogen atoms.
Moreover, Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ has the same meaning as the substituent for Y ¹ and Y ² and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group which may further have a substituent, such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group. A benzoyl group which may have a substituent or a nitro group is more preferred. Y ¹⁴ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group.

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

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

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

"Oxime ester photopolymerization initiator represented by general formula (5b)"
When Z in general formula (5) is a --CO-- group, an oxime ester photopolymerization initiator represented by general formula (5b) below is preferred.

general formula (5b)

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

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

Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) (IRGACURE OXE01), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IRGACURE OXE02) (both manufactured by BASF), N-1919 (ADEKA), TRONLY TR-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, oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. It is also possible to use an ester photopolymerization initiator.

The content of the photopolymerization initiator (E) is based on the total solid content of the photosensitive coloring composition (100 parts by mass), preferably 0.1 to 20 parts by mass, photocurable and developable From the point of view, it is more preferably 0.5 to 10 parts by mass. If it is less than 0.1 part by mass, the adhesion of the formed pattern to the base material will be poor. There is

<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" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP"(4,4'-bis(diethylamino)benzophenone, manufactured by Chemmark Chemical).

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

The content when using a sensitizer is preferably 2 to 60 parts by weight with respect to 100 parts by weight of the photoradical polymerization initiator contained in the photosensitive coloring composition. From the point of view, it is more preferably 4 to 50 parts by mass.

<thiol compound having a carboxyl group (C)>
The photosensitive coloring composition of the present invention contains a thiol compound (C) having a carboxyl group as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the process of radical polymerization 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. Therefore, a uniform cured state can be obtained at the top and bottom of the coating film, and wrinkles on the surface of the coating film due to the difference in thermal shrinkage can be suppressed even when the coating film is subsequently heat-treated. Furthermore, the inclusion of a carboxyl group improves the solubility in an alkaline developer and improves the peel developability.

The thiol compound (C) having a carboxyl group may be a compound containing one or more thiol groups and one or more carboxyl groups in one molecule. (C-1) is preferable, and a compound (C-1A) represented by the following general formula (1) is more preferable.

General formula (1)

(In general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms.)

The monofunctional thiol compound (C-1) having a carboxyl group includes 3-mercaptopropionic acid, 2-mercaptopropionic acid, thioglycolic acid and the like. A compound obtained by reacting a compound having one acid anhydride group in the molecule, such as succinic anhydride or trimellitic anhydride, with a hydroxyl group-containing monofunctional thiol may also be used.

Examples of the compound (C-1A) represented by the general formula (1) include thiomalic acid.

As the polyfunctional thiol compound (C-2) having a carboxyl group, a compound having one acid anhydride group in the molecule such as succinic anhydride or trimellitic anhydride reacts with a hydroxyl group-containing polyfunctional thiol. A compound obtained by reacting a compound having two or more acid anhydride groups in the molecule such as pyromellitic anhydride with a hydroxyl group-containing monofunctional thiol or a hydroxyl group-containing polyfunctional thiol may be used. .

[Compound having one acid anhydride group in the molecule]
Compounds having one acid anhydride group in the molecule include, for example, succinic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. acids, alkenyl succinic anhydride, 3-carboxymethylglutaric anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, trimellitic anhydride, 1,3,8-naphthalenetricarboxylic acid 1, 8-anhydride, 1,2,5-naphthalenetricarboxylic acid 1,2-anhydride and the like.

[Compound having two or more acid anhydride groups in the molecule]
Compounds having two or more acid anhydride groups in the molecule include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride anhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3 - aliphatic such as methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol trimellitic anhydride, propylene glycol trimellitic anhydride, butylene glycol trimellitic anhydride, 3,3′,4,4′ -benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3 ,3′,4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3, 3′,4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p -phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylether dianhydride, bis(triphenylphthalic acid) dianhydride, phenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-di Carboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 - naphthalene succinic dianhydride, or aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride be done.

[Hydroxyl group-containing polyfunctional thiol]
Examples of hydroxyl group-containing polyfunctional thiols include 1,2-dimercapto-3-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-butanol, 2,4-dimercapto-1-butanol, 3,4-dimercapto-1-butanol, 1,3-dimercapto-2-butanol, 1,4-dimercapto-2-butanol, 3,4-dimercapto-2-butanol, trimethylolpropane dimercaptoacetate, trimercaptopenta Erythritol, pentaerythritol tris (3-mercaptoacetate), dipentaerythritol pentakis (3-mercaptopropionate) and the like.

[Hydroxyl group-containing monofunctional thiol]
Hydroxyl group-containing monofunctional thiols include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto -1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2 -Mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

The content of the thiol compound (C) having a carboxyl group is preferably 1.0 to 10.0% in the total solid content of the photosensitive coloring composition, more preferably 1.5 to 8.0%. be. It is more preferably 2.0 to 4.0%, and within this range, wrinkles, chemical resistance and peel developability are improved. When the content is 1.0% or more, the anti-wrinkle effect is excellent, while when the content is 10.0% or less, the chemical resistance is good.

<Other thiol compounds (H)>

The photosensitive coloring composition of the present invention may contain a thiol compound (H) other than the thiol compound (C) having a carboxyl group.

Monofunctional thiols containing no carboxyl group include tritylthiol and 2-mercapto-5-methylthio-1,3,4-thiadiazole.

Polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene and ethylene groups having two or more SH groups can also be used. In this case, since the number of functional groups is increased, 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 optionally usable other thiol compounds (H) can be used singly or in combination of two or more.

<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 photosensitive coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor is increased, and the straightness of the taper, the wrinkles of the coating film, the pattern resolution, etc. are improved.

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

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

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

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

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

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

More specifically, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Corporation, Adekastab LA-29, LA-31RG, LA manufactured by ADEKA Corporation -32, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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

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

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

More specifically, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., Adekastab 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., etc. mentioned.

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

<Antioxidant>
The photosensitive coloring composition of the invention can 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 raised. Especially when the colorant concentration of the photosensitive 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 photopolymerization initiator are taken, so yellowing during the heat process is strong. phenomena can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

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

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

Hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 4,4′-butylidene-bis-(2-t -butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearylpropionate, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3, 5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2′- methylenebis(6-t-butyl-4-ethylphenol), 2,2′ thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3 ,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthio methyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-( 3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2′-thio-bis-( 6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2′-isobutylidene-bis-( 4,6-dimethyl-phenol), 2,2′-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)- Phenol and the like can be mentioned. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

More specifically, Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation, KEMINOX101, 179, 76 manufactured by Chemipro Co., Ltd. 9425, IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Corporation, Cyanox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd. is mentioned.

Hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetra methyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetra methyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2 , 2,6,6-tetramethyl-4-piperidyl methacrylate, a polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino ]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5, Ester of 5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino} -1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4 decanedioate -piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyliperidyl)[[3,5-bis(1,1dimethyl ethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl ]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2, 6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6- hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide and the like mentioned. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

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

Phosphorus antioxidants include di(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2′-methylenebis(4,6- di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'- Isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl)phosphite, diphenylisodecylphosphite, tris(isodecyl)phosphite, triphenylphosphite, tetrakis(2,4-di-t-butylphenyl)-4 ,4-biphenyldiphosphonate, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4' isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl)phosphite, 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.

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

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

More specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd., and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

When the photosensitive coloring composition of the present invention contains a leveling agent, the amount of the leveling agent added is preferably 0.001 to 2.0% by mass, more preferably 0.001 to 2.0% by mass, based on the total solid content of the composition of the present invention. is 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 leveling agent, or may contain two or more types of leveling agents. When two or more types are included, the total amount is preferably within the above range.

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

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

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

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition included in the present invention contains a coloring agent such as a pigment in a dispersing agent, a coloring agent carrier such as a binder resin, and/or a solvent, preferably with a dispersing aid (pigment derivative or surfactant). Together, it can be manufactured by finely dispersing 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 (pigment dispersion body or colorant dispersion). 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 photosensitive coloring composition. The solvent-developable or alkali-developable photosensitive coloring composition comprises the above-mentioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other dispersing aids, and It can be adjusted by mixing additives and the like. 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>
Examples of surfactants include those described for the leveling agent, and these may be used alone or in combination of two or more, but 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. .

<Solvent (N)>
The photosensitive coloring composition of the present invention contains a solvent in order to facilitate the formation of a colored film by coating it on a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected in consideration of good applicability of the photosensitive coloring composition, solubility of each component of the photosensitive coloring composition, and safety.

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

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

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

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenetol, methylanisole and the like.

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

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. etc.

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

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

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

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

<Removal of coarse particles>
The colored dispersion or the photosensitive colored composition of the present invention is separated into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.1 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, or the like. It is preferable to remove coarse particles of 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.

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

<Manufacturing method of color filter>
A color filter can be manufactured by a printing method or a photolithography 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 photosensitive coloring composition prepared as the solvent development type or alkali development type coloring resist material is applied onto the transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. It is applied so that the dry film thickness is 0.2 to 5 μm by the application method of . 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 photolithographic method, it is possible to manufacture a color filter with higher accuracy than the printing method.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an 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.

<Liquid crystal display device>
A liquid crystal display device having the color filter of the present invention will be described.
A liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. As a light source, a cold cathode fluorescent lamp (CCFL) and a white LED can be used. In the present invention, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC sealed between them.

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

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

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

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

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

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

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

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively.

Prior to Examples, calculation methods for measuring the weight-average molecular weight of the resin and the method for measuring the acid value of the resin will be described.

(Average molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as an apparatus, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used as both packing materials, and the oven temperature was 40. °C, a THF solution was used as an eluent, and the flow rate was 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalent values.

(Acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution and stir to dissolve uniformly. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

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

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

<Polymerizable compound (B)>
The following compounds were used as the polymerizable compound (B).

Dipentaerythritol penta and hexaacrylate (B-1)
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
Polyfunctional urethane acrylate (B-2)
[Polyfunctional urethane acrylate (B-2) was prepared as follows. 432 g of pentaerythritol triacrylate and 84 g of hexamethylene diisocyanate were charged into a five-necked reaction vessel having an internal volume of 1 liter and reacted at 60° C. for 8 hours to produce a polyfunctional urethane acrylate (B-2) having an acryloyl group. got stuff The proportion of the polyfunctional urethane acrylate (B-2) in the product was 70% by mass, and the remainder was occupied by other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate group was present in the reaction product. ]

<Thermosetting compound (F)>
The following compounds were used as the thermosetting compound (F).

(Epoxy compound (F-1))
1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2′-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel Corporation)],
Glycidyl etherified epoxy compounds of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
Equal amounts of triglycidyl isocyanurate were mixed to prepare an epoxy compound (F-1).

<Photoinitiator (E)>
The following compounds were used as the photopolymerization initiator (E).

(2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) (E-1)
[Omnirad 369E (manufactured by IGM Resins B.V.)]
A compound (E-2) represented by the chemical formula (4b-1)

<Sensitizer (G)>
The following compounds were used as the sensitizer (G).
2,4-diethylthioxanthone (G-1)
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]

<Monofunctional thiol compound having a carboxyl group (C-1)>
The following compounds were used as the monofunctional thiol (C-1) having a carboxyl group.
3-mercaptopropionic acid (C-1-1)
[Manufactured by Tokyo Chemical Industry Co., Ltd.]
Thioglycolic acid (C-1-2)
[Manufactured by Tokyo Chemical Industry Co., Ltd.]
Thiomalic acid (C-1-3)
[Manufactured by Tokyo Chemical Industry Co., Ltd.]

<Polyfunctional thiol compound having a carboxyl group (C-2)>
[The polyfunctional thiol compound (C-2) having a carboxyl group was prepared as follows. 10.8 parts of 3-mercapto-1,2-propanediol, 10.9 parts of pyromellitic anhydride, mono-n-butyl tin (IV ) 0.01 part of oxide and 32.6 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride was half-esterified by measuring the acid value, it was cooled and taken out as a 40% solution of polyfunctional thiol (C-2-1). ]

<Other thiol compounds (H)>
The following compounds were used as other thiol compounds (H).
Pentaerythritol tetrakis(3-mercaptopropionate) (H-1)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
Tritylthiol (H-2)
[Manufactured by Tokyo Chemical Industry Co., Ltd.]

<Leveling agent (I)>
The following compounds were used as the leveling agent (I).
"BYK-330" manufactured by BYK Chemie Co., Ltd.: 1 part "Megafac F-551" manufactured by DIC Corporation: 1 part "Emulgen 103" manufactured by Kao Corporation: 1 part Mixed solution dissolved in 97 parts of propylene glycol monomethyl ether acetate (I-1).

<Solvent (N)>
Propylene glycol monomethyl ether acetate: 30 parts Cyclohexanone: 30 parts Ethyl 3-ethoxypropionate: 10 parts Propylene glycol monomethyl ether: 10 parts Cyclohexanol acetate: 10 parts Dipropylene glycol methyl ether acetate: 10 parts and mixed to obtain a solvent (N-1).

<Green pigment (A)>
(Production of micronized green pigment (A-1))
phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 ("FASTOGENGREEN A110" manufactured by DIC), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product is put into 8000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night. , to obtain a finely divided green pigment (A-1).

(Preparation of micronized green pigment (A-2))
phthalocyanine green pigment C.I. I. Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. bottom. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided green pigment (A-2).

(Production of micronized green pigment (A-3))
500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (6), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added to a three-necked flask and stirred at 20°C. , was allowed to react for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. ℃ and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain a finely divided green pigment (A-3), which is a phthalocyanine green pigment.

Formula (6)

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

(Preparation of finely divided yellow pigment (J-2))
Metal complex yellow pigment C.I. I. 500 parts of Pigment Yellow 150 ("E4GN" by Lanxess), 2500 parts of sodium chloride and 250 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 100°C for 6 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided yellow pigment (J-2).

<Production of resin type dispersant solution (L)>
LPN21116 manufactured by BYK, which is a commercially available resin-type dispersant, was mixed with propylene glycol monomethyl ether acetate to prepare a solution having a non-volatile content of 20% by mass, thereby obtaining a resin-type dispersant solution (L-1).

<Method for producing pigment dispersion>
(Pigment Dispersion (P-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 pigment dispersion (P-1).
Micronized green pigment (A-1): 14.0 parts Resin type dispersant solution (L-1): 15.0 parts Binder resin (D-1) solution: 15.0 parts Propylene glycol monomethyl ether acetate (solvent ): 56.0 copies

(Pigment dispersion (P-2 to 5))
Pigment dispersion (P-1) was carried out in the same manner as pigment dispersion (P-1), except that the pigment, resin-type dispersant solution, binder resin solution, and solvent were changed to the compositions and blending amounts (parts by mass) shown in Table 2. Dispersions (P-2 to 5) were prepared respectively.

[Example 1]
(Photosensitive coloring composition (M-1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (M-1).
Pigment dispersion (P-1): 28.0 parts Pigment dispersion (P-4): 6.0 parts Pigment dispersion (P-5): 6.0 parts Monofunctional thiol having a carboxyl group (C-1 -1): 0.4 parts binder resin (D-2): 11.0 parts polymerizable compound (B-2): 4.0 parts photopolymerization initiator (E-1): 0.2 parts photopolymerization Initiator (E-2): 0.2 parts Thermosetting compound (F-1): 0.1 parts Sensitizer (G-1): 0.1 parts Leveling agent (I-1): 1. 0 parts solvent (N-1): 43.0 parts

[Examples 2 to 12, Comparative Examples 1 to 3]
(Photosensitive coloring composition (M-2 to 15))
The composition shown in Table 3, and except for changing the amount (parts by weight) of the photosensitive coloring composition (M-1) of Example 1, were performed in the same manner as in Examples 2 to 12 and Comparative Examples 1 to 3. A natural coloring composition (M-2 to 15) was obtained, respectively. It should be noted that Examples 1, 2, and 12 in this specification are reference examples.

<Evaluation of photosensitive coloring composition>
Coating films of the obtained photosensitive coloring compositions (M-1 to M-15) were tested by the following method. Table 4 shows the results of the test. In the following evaluation results, ⊚, ◯, and Δ indicate practical use, and × indicate non-practical use.

[Wrinkle]
The resulting photosensitive coloring composition is applied onto a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater, then dried at 70°C for 20 minutes, and then dried using an ultra-high pressure mercury lamp. It was exposed to ultraviolet rays at an integrated light amount of 150 mJ/cm@2 and developed with an alkaline developer at 23.degree. Then, it was heated at 220° C. for 30 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrates were made to have film thicknesses of 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm and 3.0 μm after heat treatment at 220°C. Using an optical microscope, wrinkles on the surface of the coating film thus obtained were observed at a magnification of 200, and evaluated according to the following criteria. × is a level that is difficult to use.
◎: No wrinkles even at 3.0 μm
○: Wrinkles occur in the coating film of 2.0 μm or more
×: Wrinkles occur with a coating film of 1.0 μm or more (difficult to use)

[chemical resistance]
The resulting photosensitive coloring composition is applied onto a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater, then dried at 70°C for 20 minutes, and then dried using an ultra-high pressure mercury lamp. It was exposed to ultraviolet rays at an integrated light amount of 150 mJ/cm@2 and developed with an alkaline developer at 23.degree. Then, it was heated at 220° C. for 30 minutes and allowed to cool to obtain a coated substrate. The prepared coated substrates were matched to a chromaticity of y=0.600 after heat treatment at 220°C. Chromaticity ([L * (1), a * (1), b * (1)]) of the resulting coating film at C light source is measured with a microscopic spectrophotometer (manufactured by Olympus Optical Co., Ltd. "OSP-SP100"). was measured using Furthermore, after that, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, and then the 1-methyl-2-pyrrolidone was washed with pure water. [L*(2), a*(2), b*(2)]) were measured, and the color difference ΔE*ab was calculated according to the following formula and evaluated according to the following criteria. × is a level that is difficult to use.
ΔE*ab=[[L*(2)-L*(1)]2+[a*(2)-a*(1)]2+[b*(2)-b*(1)]2]1/ 2
◎: ΔE*ab is less than 1.5
○: ΔE*ab is 1.5 or more and less than 3.0
△: ΔE*ab is 3.0 or more and less than 5.0
×: ΔE*ab is 5.0 or more (difficult to use)

[Peeling developability]
The resulting photosensitive coloring composition is applied onto a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater, then dried at 70°C for 20 minutes, and then dried using an ultra-high pressure mercury lamp. It was exposed to ultraviolet rays at an integrated light amount of 150 mJ/cm@2 and developed with an alkaline developer at 23.degree. The state of development of the unexposed area was observed and evaluated according to the following criteria. × is a level that is difficult to use.
◎: No flakes
○: Peeled pieces dissolved in less than 5 seconds
×: It takes 5 seconds or more to dissolve the peeled pieces (difficult to use)

As can be seen from the results in Table 4, Examples 1 to 12 were excellent in terms of wrinkles on the surface of the coating film, chemical resistance, and peel developability, and had practicality.
On the other hand, Comparative Examples 1 to 3 were practically difficult.

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

Claims (5)

Green pigment (A), polymerizable compound (B), thiol compound (C) having a carboxyl group (excluding monofunctional thiol having a carboxyl group having an aromatic ring), binder resin (D), and photopolymerization initiation containing an agent (E),
A photosensitive coloring composition for a color filter, wherein the thiol compound (C) having a carboxyl group is a compound (C-1A) represented by the following general formula (1).
General formula (1)

(In general formula (1), R ¹ is an alkylene group having 1 to 10 carbon atoms.) The color filter according to claim 1, wherein the content of the thiol compound (C) having a carboxyl group is 1.0% by mass or more and 10.0% by mass or less with respect to the total solid content of the photosensitive coloring composition. A photosensitive coloring composition for 3. The photosensitive coloring composition for color filters according to claim 1 , wherein the polymerizable compound (B) is a polyfunctional urethane acrylate. A color filter comprising a green filter segment formed from the photosensitive coloring composition for a color filter according to any one of claims 1 to 3 on a substrate. A liquid crystal display device comprising the color filter according to claim 4 .

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