JP2021004922A - Photosensitive coloring composition, and color filter and liquid-crystal display using the same - Google Patents

Abstract

To provide: a photosensitive coloring composition for a color filter capable of forming a favorable pixel, where the composition realizes an excellent pattern shape of the pixel and can form a coating film that causes little discoloration (little water infiltration) even if exposed to an alkaline solution; and a color filter formed using the same.SOLUTION: A photosensitive coloring composition includes a colorant (A), a polymerizable compound (B), a binder resin (C), a photoinitiator (D), a thiol-based compound (E) including a thiol-based compound (E1) represented by the chemical formula in the figure, and a fluorine-based leveling agent (F).SELECTED DRAWING: Figure 1

Description

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

The color filter is arranged on a transparent substrate such as a glass substrate by arranging two or more kinds of fine band-shaped filter segments (hereinafter, also referred to as coating films) having different hues in parallel (striped shape) or intersecting each other. Or, two or more kinds of fine filter segments having different hues are arranged so as to be arranged in order in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of a few microns to a few hundreds of microns and are neatly arranged in a predetermined arrangement for each hue.
Currently, as a method for manufacturing a color filter, a method called a pigment dispersion method, which uses a pigment having excellent resistance such as light resistance and heat resistance as a coloring material, is the mainstream. In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed in a pattern corresponding to a filter segment of a certain color. Next, the unexposed portion of the coating film is removed by development, and then treatment such as heating is performed as necessary. As a result, the filter segment pattern of the first color is obtained. Then, by performing the same operation as this, a filter segment pattern of another color is formed, and the color filter is completed.

When the color filter is formed, if it is exposed to an alkaline aqueous solution used as a developing solution, the color resist pattern may be discolored (water stain). As a countermeasure, Patent Document 1 contains a fluorine-based surfactant. The method used is disclosed. Further, Patent Document 2 discloses a method for preventing uneven development (water stain) using a polymerizable compound having a specific structure.

JP-A-2016-102212 Japanese Unexamined Patent Publication No. 2014-48556

An object of the present invention is to achieve the following object.
That is, an object of the present invention is to obtain a coating film having an excellent pattern shape when formed into pixels and having reduced discoloration of the coating film (less likely to cause water stains) even when exposed to an alkaline solution. It is an object of the present invention to provide a photosensitive coloring composition for a color filter capable of forming various pixels, and further to provide a color filter formed by using the photosensitive coloring composition.

That is, the present invention includes a colorant (A), a polymerizable compound (B), a binder resin (C), a photopolymerization initiator (D), a thiol compound (E), and a fluorine-based leveling agent (F). The present invention relates to a photosensitive coloring composition, wherein the thiol-based compound (E) contains a thiol-based compound (E1) represented by the following general formula (1).

General formula (1)

(In the general formula (1), R is an n-valent organic group, and n is an integer of 1 to 4.)

Further, in the present invention, the fluorine-based leveling agent (F) is an ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group and / or a poly (perfluoroalkylene ether) chain, and other ethylenically unsaturated monomers. The present invention relates to the above-mentioned photosensitive coloring composition, which comprises a copolymer (FD) of a saturated monomer (FD2).

Further, the present invention is characterized in that the thiol compound (E1) represented by the general formula (1) is contained in an amount of 0.1 to 7.5% by mass based on the total non-volatile content of the coloring composition. With respect to the sex coloring composition.

The present invention further relates to the above-mentioned photosensitive coloring composition, wherein the thiol-based compound (E) contains a thiol-based compound (E2) other than the thiol-based compound (E1).

The present invention also relates to a color filter composed of a base material and a filter segment formed by using the above-mentioned photosensitive coloring composition.

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

By using the photosensitive coloring composition of the present invention, each color filter segment without discoloration can be formed. Therefore, a high-quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

FIG. 1 shows a form of a color filter of the present invention.

The terminology of the present specification is defined. Unless otherwise specified, the terms "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are used, respectively. , "Acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid". As used herein, "CI" means a color index (CI). Colorants include pigments and dyes.

<Colorant (A)>
The photosensitive coloring composition of the present invention contains a pigment or a dye as the colorant (A).
As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more. As the pigment, a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by color index numbers.

Examples of the red pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 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 and 282, 283, 284, 285, 286, 287, 291, 295, 296 and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, 295, 296, more preferably C.I. I. Pigment Red 177, 254, 291, 295, 296.

Further, the red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments and / or the yellow pigments described below may be used in combination.

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned. 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. Further, the purple pigment described later may be used in combination with the blue coloring composition.

Examples of the purple pigment 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 can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of the green pigment include C.I. I. Pigment Green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,37,45,48,50,51,54,55,58,59,62, 63 and the like can be mentioned, but the present invention is 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 yellow pigment described later may be used in combination with the green coloring composition.

For yellow pigments, 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 233 and the like. Preferably C.I. I. Pigment Yellow 138, 139, 150, 185, 231 and 233.

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

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

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark 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 coatability, sensitivity, developability, etc. while balancing saturation and lightness.

<Pigment miniaturization>
When an organic pigment is used as the colorant, it is preferable to perform a miniaturization treatment and then mix it with another raw material. Examples of the miniaturization treatment method include wet grinding, dry grinding, dissolution and precipitation, and the like. Among these, salt milling treatment by the kneader method, which is a kind of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. With an appropriate particle size, the dispersibility is further improved and the contrast ratio of the coating film is further improved. The average primary particle diameter is an average value of about 20 particles arbitrarily selected from a magnified image of a TEM (transmission electron microscope). If there is a vertical axis length and a horizontal axis length of the particles, the vertical axis length is used.

The salt milling treatment is a batch type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, for example, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer or the like. This is a process in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a continuous kneader. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve a water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120 ° C. or higher because it is difficult to volatilize due to a temperature rise during salt milling. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, and the like. 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, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

Resin can be added as needed during the salt milling process. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Dye>
Examples of the dye include acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, construction dyes, sulfide dyes and the like. In addition, a derivative of a dye and a rake pigment obtained by raked a dye can also be mentioned.

The dye is an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of the acidic dye; an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a primary amine compound; a resin component having these amino groups and a salt-forming compound such as an acidic dye can be mentioned. A salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness. The compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include organic acids, perchloric acids, and salt-forming compounds with these metal salts. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

The chemical structure of the dyes is, for example, azo dyes, disazo dyes, azomethine dyes (Indoaniline dyes, Indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes). Dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , Polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples thereof include dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Kinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable. The specific structure of dyes is "New Edition Dye Handbook" (edited by Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colorists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986). It is described in.

<Dye derivative>
A dye derivative can be used for the coloring composition, if necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt, a sulfonamide group, or a tertiary amino group at the terminal thereof. Examples thereof include compounds and compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indol, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, the diketopyrrolopyrrole dye derivatives are JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine-based. The dye derivatives are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, Patent No. 5735266, and the anthraquinone-based dye derivatives are JP-A-63-246674, JP-A-09. -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, quinacridone-based dye derivatives are JP-A-48-54128, JP-A-03-9961 and JP-A-2000-273383, Dioxazine-based dye derivatives are JP-A-2011-162662, and thiazineindigo-based dye derivatives are JP-A-2007-314785, Triazine-based dye derivatives. Is JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681. , Benzoisoindole-based dye derivatives are JP-A-2009-57478, and quinophthalone-based dye derivatives are JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012. -226110, naphthol dye derivatives are JP2012-208329, JP2014-5439, and azo dye derivatives are JP2001-172520, JP2012-1722092, acidic. Substituents are referred to in JP-A-2004-307854, and basic substituents are referred to in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Examples include the described dye derivatives. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group or a basic group. , A compound having a substituent such as a neutral group is synonymous with a dye derivative.

These dye derivatives can be used alone or in combination of two or more.

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 pacing, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the pigment surface and the pigment derivative is not added. In comparison, the primary particles of the pigment can be made finer.

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

<Resin type dispersant>
A known resin-type dispersant can be used for the photosensitive coloring composition of the present invention. The resin-type dispersant has a colorant-friendly moiety having a property of adsorbing to the additive colorant and a moiety compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed in the colorant carrier. Anything that has a function of stabilizing the substance may be used. Specifically, a urethane dispersant such as polyurethane, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, and a polycarboxylic acid (partial) amine Salts, ammonium polycarboxylic acid salts, alkylamine polycarboxylic acid salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modifications, poly (lower alkyleneimine) and free carboxyl groups Oily dispersants such as amides and salts thereof formed by reaction with polyesters having (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-malein Water-soluble resins such as acid copolymers, polyvinyl alcohols and polyvinylpyrrolidones, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphoric acid esters, etc. are used. Can be used alone or in combination of two or more.
Examples of the polymer dispersant having a basic functional group include a nitrogen atom-containing graft copolymer and a nitrogen atom-containing functional group having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples thereof include acrylic block copolymers and urethane polymer dispersants.

The resin type dispersant is preferably used in an amount of about 3 to 200% by mass with respect to the total amount of the colorant, and more preferably about 5 to 100% by mass from the viewpoint of film forming property.

<Binder resin (B)>
The coloring composition of the present specification contains a binder resin (B). The binder resin is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, a thermoplastic resin, a thermosetting resin, an active energy ray curable resin, and the like. The active energy ray-curable resin may have an active energy ray-reactive functional group in the thermoplastic resin or the thermosetting resin. Further, as the binder resin, an alkali-soluble resin is preferable from the viewpoint of developability in terms of physical properties. Alkali solubility is for imparting development solubility in the alkali development step at the time of producing a color filter, and an acidic group is required.

The binder resin can be used alone or in combination of two or more.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
The thermoplastic resin is, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, etc. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble thermoplastic resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (maleic anhydride) copolymer and the like. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the methods (i) and (ii) shown below. Due to the effect of the active energy rays, the resin is three-dimensionally crosslinked to increase the crosslink density and improve the chemical resistance.

[Method (i)]
In the method (i), for example, an ethylenically unsaturated monomer having an ethylenically unsaturated monomer is copolymerized with another monomer to form a side chain epoxy group of the copolymer. The carboxyl group of an unsaturated monobasic acid having a double bond is added and reacted. Next, it is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by reacting the generated hydroxyl group with a polybasic acid anhydride.

Ethylene 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 the like. And 3,4-epoxycyclohexyl (meth) acrylates. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with unsaturated monobasic acid.

Unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, cyano-substituted products and the like. Examples include carboxylic acid.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride was used to remain. It is also possible to hydrolyze the anhydride group.

As a method similar to the method (i), for example, an ethylenically unsaturated monomer having a carboxyl group and another monomer are copolymerized with a part of the side chain carboxyl group of the copolymer obtained. This is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by subjecting an ethylenically unsaturated monomer having an epoxy group to an addition reaction.

[Method (ii)]
In the method (ii), the ethylenically unsaturated monomer having an isocyanate group is added to the side chain hydroxyl group of the copolymer obtained by copolymerizing the ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method of reacting a monomeric isocyanate group.

The ethylenically unsaturated monomer having a hydroxyl group includes, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and the like. Examples thereof include hydroxyalkyl methacrylates such as glycerol mono (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide with hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. Be done.

Other monomers that can constitute the alkali-soluble resin include N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphoric acid ester group-containing ethylenically unsaturated monomers in addition to the other ethylenically unsaturated monomers described above. Examples thereof include monomers and carboxyl group-containing ethylenically unsaturated monomers.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-. 4-Methyl-3-maleimidecoumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimoleimide, N, N'-1,4-phenylenedi maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitro) Phenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, Examples thereof include N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, and 9-maleimide acrydin. The alkyleneoxy group-containing monomer includes, for example, EO-modified cresol acrylate, n-nonylphenoloxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, and paracumylphenol. Examples thereof include EO or propylene oxide (PO) modified (meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomer already described can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. is there.

<Alkali-soluble resin without ethylenically unsaturated double bond>
The coloring composition of the present specification may contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film.

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 3,000 or less, preferably 4,000, in order to impart alkali development solubility. More preferably 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 70 or more and 180 or less, and more preferably 90 or more and 170 or less. The range. If the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

Each raw material used for synthesizing the binder resin can be used alone or in combination of two or more.

<Thermosetting compound>
In the present invention, the binder resin can be used in combination with a thermoplastic resin to further contain a thermosetting compound. When a color filter is produced using the coloring composition for a color filter of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, and thus the heat resistance of the filter segment is increased. This is improved, pigment aggregation during firing of the filter segment is suppressed, and the contrast ratio is improved.

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

<Polymerizable compound (C)>
The photosensitive coloring composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) contains a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

The polymerizable compound (C) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl. (Meta) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate , Phenoxytetraethylene glycol (meth) acrylate, Phenoxyhexaethylene glycol (meth) acrylate, Trimethylolpropane PO-modified tri (meth) acrylate, Trimethylolpropane EO-modified tri (meth) acrylate, Isocyanuric acid EO-modified di (meth) acrylate , Isocyanuric acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (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, tricyclodecanyl (meth) acrylate , (Meta) acrylic acid ester of methylolated melamine, various acrylic acid esters and methacrylate esters such as epoxy (meth) acrylate and urethane acrylate, (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 and the like.

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

The photopolymerizable monomer having an acid group is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl 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-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Polymeric compound having urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate having a hydroxyl group by reacting an alcohol with a polyfunctional isocyanate. Examples thereof include a polyfunctional urethane acrylate obtained by the above-mentioned.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Glyoxide dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of epoxy group-containing compound and carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate and the like.

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

The polymerizable compound (C) can be used alone or in combination of two or more.

The blending amount of the polymerizable compound (C) is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is blended, curability and developability are further improved.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-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- Acetphenone compounds such as butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, Benzophenone compounds such as acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 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 (trichloro) Methyl) -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- (naphtho-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-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 etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxime ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphorquinone , Ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferable.

The photopolymerization initiator (D) can be used alone or in combination of two or more.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. To.

Oxime ester compounds are described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Examples thereof include ester-based photopolymerization initiators.

The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

<Sensitizer>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, anurene derivative, spiropirane derivative, spiroxazine derivative, thiospiropirane derivative, metal arene complex, organic ruthenium complex, or Michler ketone derivative, α- Achilloxyester, acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4, Examples thereof include 4'-tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Among the above sensitizers, examples of the sensitizer that can be particularly preferably sensitized include a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative. 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.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

The sensitizer can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, curability and developability are further improved.

<Thiol compound (E)>
The photosensitive coloring composition of the present invention contains a thiol-based compound (E1) represented by the formula (1).
The thiol compound (E) is also used as a curing agent for epoxy resins, chain transfer agents, photocurable monomers, cross-linking agents, adhesion improvers, etc., and is effective in reducing water stains, which is a subject of the present invention. It is important to include the thiol-based compound (E1) to be exhibited, and the other thiol-based compound (E2) may also have other performances.

<Thiol compound (E1)>
General formula (1)

(In the general formula (1), R is an n-valent organic group, and n is an integer of 1 to 4.)
The n-valent organic group of R includes a 1- to 4-valent group corresponding to an alkyl group having 1 to 20 carbon atoms, a 1 to 4-valent group corresponding to an aryl group having 6 to 20 carbon atoms, and a 5-atom atomic number. A 1 to 4 valent group corresponding to 20 heteroaryl groups, a 1 to 4 valent group corresponding to a heteroaryl group having 5 to 20 atoms, and a 1 to 4 valent group corresponding to an alkyl group having 1 to 20 carbon atoms. Examples include a group in which a group is combined. As n, 2 to 4 are preferable.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, an o-kisilyl group and the like. Examples of the heteroaryl group having 5 to 20 atoms include a pyrazole group, an imidazole group, a tetrazole group, a triazine group, an isocyanul group and the like.

The thiol compound (E1) is preferably 1,4-bis (3-mercaptobutylyloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine. -2,4,6 (1H, 3H, 5H)-Trione, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate). These can be used alone or in combination of two or more.

The thiol compound (E1) represented by the general formula (1) is preferably contained in an amount of 0.1 to 7.5% by mass based on the total non-volatile content of the coloring composition.

<Thiol compound (E2)>
A thiol-based compound (E2) other than the thiol-based compound (E1) can be used in combination with the photosensitive coloring composition of the present invention. Examples of the thiol compound (E2) include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bis. Thiopropionate, Trimethylol Propanethiol Thiolthioglycolate, Trimethylol Propanethiol Thiolthiopropionate, Trimethylol Propanethiol (3-mercaptobutyrate), Pentaerythritol Tetraxthioglycolate, Pentaerythritol Tetraxthiopropionate, Tri Tris (2-hydroxyethyl) mercaptopropionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto -S-Triazine, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and other mercaptos, trimethylolpropanedipropanethiol, pentaerythritol dipropanethiol, pentaerythritol tripropanethiol, pentaerythritol tetrapropanethiol and the like Preferably, ethylene glycol bisthiopropionate, trimethylrolpropanthiotripropionate, pentaerythritol tetrakisthiopropionate, trimethylrolpropandipropanethiol, pentaerythritol dipropanethiol, pentaerythritol tripropanethiol. , Pentaerythritol tetrapropanethiol.

<Polymerization inhibitor>
The photosensitive coloring composition may contain a polymerization inhibitor. As a result, exposure to the mask due to diffracted light can be suppressed during exposure by the photolithography method, so that a pattern having a desired shape can be easily obtained.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-. Propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4- Alkyl catechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkyl resorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkyl hydroquinone compounds such as 2,5-di-tert-butyl hydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles of the coating film, pattern resolution and the like are improved.

<UV absorber>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. ..

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

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 non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and 2- [2-hydroxy-3,5. -Bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-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-benzotriazole-2-yl)-(1,1-dimethyl) Ethyl) -4-hydroxy, a mixture of C7-9 side chains and linear alkyl esters, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3-( Reaction product of 2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole-2-yl) -4- (1,1) , 3,3-Tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2 -(2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-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-benzotriazole-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-) 2H-benzotriazole-2-yl) phenyl] propionate can be mentioned. In addition, oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

Examples of triazine 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-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4- Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) Oxy) Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6-tris (2-Hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2'-di-hydroxy-4-methoxybenzophenone. 2,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadeciloxybenzophenone, 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.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl 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 present invention may contain an antioxidant. Antioxidants are used to reduce the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during heat curing or ITO annealing. Can be improved. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film cross-linking component decreases, so that the yellowing of the thermal process becomes stronger due to the use of a highly sensitive cross-linking component and the increase in the amount of the photopolymerization initiator. Can be seen. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

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

The antioxidant can be used alone or in combination of two or more.

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

<Fluorine-based surfactant (F)>
The photosensitive coloring composition of the present invention contains a fluorine-based surfactant (F) in order to reduce water stains. Examples of the fluorine-based surfactant (F) include surfactants having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain, and among them, for example, Japanese Patent Application Laid-Open No. 2018-25687. An ethylenically unsaturated monomer (FD1) containing an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain and another ethylenically unsaturated monomer (FD2) described in the publication. It is more preferable to include one composed of the copolymer (FD) of. Further, the other ethylenically unsaturated monomer (FD2) preferably has an adamantyl group.

Examples of the method for producing the compound (FD) include a method of polymerizing using a polymerization initiator in an organic solvent. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers and hydrocarbons are preferable, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate and butyl acetate, Examples thereof include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility and polymerizable property. Examples of the polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Further, if necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglyco-lic acid, and octyl thioglyco-lic acid can be used.

As the ethylenically unsaturated monomer (FD1) containing a fluorinated alkyl group constituting the compound (FD), for example, those represented by the following general formula (L1) can be preferably exemplified.
General formula (L1)

[In the above general formula (L1), R represents a hydrogen atom or a methyl group, L represents any one group of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf). -1) Represents any one group of (Rf-7). ]

(N in the above formulas (L-1) and (L-3) to (L-7) represents an integer of 1 to 8. M in the above formulas (L-8) to (L-10) is 1. Represents an integer of ~ 8, and n represents an integer of 0 to 8.
Rf'' in the above formulas (L-6) and (L-7) represents any one group of the following formulas (Rf-1) to (Rf-7). )

N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. In the above formula (Rf-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1-5, n is an integer of 0-4, and the sum of m and n is 4-5. In the above equation (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, and p is an integer of 0 to 5. Moreover, the total product of m, p and n and l is 2 to 71. Preferably, m is an integer of 1-3, n is an integer of 1-3, l is an integer of 1-6, p is an integer of 0-2, and m, p and n. The sum of the products of and l is 2-23.

Among the ethylenically unsaturated monomers (FD1) containing an alkyl fluorinated group, a fluorothermally decomposable resin exhibiting excellent smoothness can be obtained. Therefore, a carbon atom to which a fluorine atom is directly bonded can be obtained. A monomer having a fluorinated alkyl group having a number of 1 to 6 is preferable, and a monomer having a fluorinated alkyl group having a carbon atom number of 4 to 6 to which a fluorine atom is directly bonded is more preferable.

The ethylenically unsaturated monomer (FD1) containing a poly (perfluoroalkylene ether) chain constituting the compound (FD) includes a divalent fluorocarbon group having 1 to 3 carbon atoms and an oxygen atom. Examples thereof include those having a structure in which they are connected alternately.

Further, the other ethylenically unsaturated monomer (FD2) constituting the compound (FD) is preferably a monomer having an adamantyl group, and further suppression of water stain can be expected.

The amount of the fluorine-based surfactant added to the photosensitive coloring composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005, based on the total solid content of the composition of the present invention. ~ 1.0% by mass. Within this range, the balance between the coatability of the coloring composition, the pattern adhesion, and the transmittance is good. The photosensitive coloring composition of the present invention may contain two or more kinds including other non-fluorine-based surfactants. When two or more types are included, the total amount is preferably in the above range.

Silicone-based surfactants can be used as non-fluorine-based surfactants, and nonionic surfactants, cationic surfactants, and anions classified according to their properties, including non-fluorine-based surfactants. Various surfactants such as sex surfactants can be used.

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

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

Adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-. (Meta) acrylic silanes such as metharoxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-) Aminosilanes such as butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, p-styryltrimethoxysilane Such as styryls, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis (triethoxysilylpropyl) tetrasulfide, and silane coupling agents such as isocyanates such as 3-isocyanvopropyltriethoxysilane. Be done. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition. It is more preferable because the effect is large within this range and the balance between adhesion, resolution and sensitivity is good.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition contained in the present invention comprises a colorant in a colorant carrier such as a dispersant or binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant). It can be manufactured by finely dispersing using various dispersion means such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). .. At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. There is no need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other dispersion aids, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Solvent>
The coloring composition of the present invention contains a solvent so as to be applied on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm to facilitate the formation of a coloring film. The solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

As the solvent, a solvent usually used in the art can be used, and in consideration of performance such as boiling point, SP value, evaporation rate, viscosity, etc., it may be used alone or as appropriate according to the coating conditions (speed, drying conditions, etc.). Used as a mixture.

Examples of the solvent used include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and not containing -COO-). , Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (OH in the molecule) Included, -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

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 coatability and drying property. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferable.

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

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

<Manufacturing method of color filter>
It is preferable that the color filter first forms a black matrix on the substrate and then forms a filter segment. A thin film transistor (TFT) can be formed on the base material in advance, and then a black matrix can be formed.
Examples of the black matrix include a multilayer film of chromium and chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed.

The filter segment can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like.
In the printing method, a pattern can be formed only by repeating printing and drying of the photosensitive coloring composition prepared as a printing ink, so that the color filter is excellent in mass productivity at low cost as a manufacturing method. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

In the electrodeposition method, a transparent conductive film formed on a transparent substrate is used, and filter segments of each color are electrodeposited on the transparent conductive film by electrophoresis of colloidal particles to prepare a color filter. Further, in the transfer method, a filter segment is formed on the peeled surface of the peelable sheet. Next, this filter segment is transferred to a transparent substrate to prepare it.

In the photolithography method, for example, a photosensitive coloring composition containing a colorant having a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiation) through a mask having a predetermined pattern. Then, the developer is immersed in a solvent or an alkaline developer, or the developer is sprayed with a spray or the like for development, and the uncured portion is removed to obtain a desired pattern. By performing this step in the same manner using a photosensitive coloring composition having a colorant having another color tone, a color filter having filter segments of each color can be produced. Further, a second film (oxygen blocking film) can be further formed on the first film before exposure by using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film is not in contact with oxygen, so that the exposure sensitivity is further improved. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment. The photolithography method is preferable because it can produce a color filter with higher accuracy than the printing method.

Examples of the coating apparatus include spray coating, spin coating, slit coating, roll coating and the like. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. In addition, a defoaming agent or a surfactant can be added to the developing solution.

In the color filter of the present invention, a sealing agent is used to bond the liquid crystal to the opposing substrate, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convencend bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as).

In the present specification, the color filter can be used for applications such as a solid-state image sensor, an organic EL display device, a quantum dot display device, electronic paper, and a head-mounted display, in addition to the liquid crystal display device.

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

The liquid crystal LC is oriented 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, for example, ITO is formed on the TFT (thin film transistor) array 12. 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 the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on the transparent protective film (not shown), and the alignment layer 24 covers the transparent electrode layer 23. Is provided.

Further, 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, and the wavelength at which the emission intensity is maximized in the range of 430 nm to 485 nm ( It has λ3), has a wavelength (λ4) that maximizes the emission intensity in the range of 530 nm to 580 nm, has a wavelength (λ5) that maximizes the emission intensity in the range of 600 nm to 650 nm, and has a wavelength. The ratio of emission intensity I3 at λ3 to emission intensity I4 at wavelength λ4 (I4 / I3) is 0.2 or more and 0.4 or less, and the ratio of emission intensity I3 at wavelength λ3 to emission intensity I5 at wavelength λ5 (I5 / I3). ) Is 0.1 or more and 1.3 or less, and has a white LED light source (LED1) and a wavelength (λ1) that maximizes emission intensity in the range of 430 nm to 485 nm, and is in the range of 530 nm to 580 nm. Spectral characteristics having a second emission intensity peak wavelength (λ2) inside, 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) having a wavelength is preferable.

Specific examples of the LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of the LED2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

Hereinafter, the present invention will be described with reference to Examples. In addition, "part" and "%" in an Example represent "mass part" and "mass%" respectively.

Prior to the embodiment, a method of calculating the weight average molecular weight of the resin and the method of measuring the acid value of the resin will be described.

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

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

(Ammonium salt value of resin having a cationic group in the side chain)
The ammonium salt value of the resin having a cationic group in the side chain is a value obtained by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator and then converting it into an equivalent amount of potassium hydroxide. , Indicates the ammonium salt value of the non-volatile component.

<Manufacturing of refined pigments>
(Miniaturized pigments A-1 to 5)
The finely divided aluminum phthalocyanine pigments (A-1 to 5) of the following formulas 2 to 6 were produced according to the examples of JP-A-2017-11138. The structure is shown below.

(Miniaturized Aluminum Phthalocyanine Pigment A-1)
Equation (2)

(Miniaturized Aluminum Phthalocyanine Pigment A-2)
Equation (3)

(Miniaturized Aluminum Phthalocyanine Pigment A-3)
Equation (4)

(Miniaturized Aluminum Phthalocyanine Pigment A-4)
Equation (5)

(Miniaturized Aluminum Phthalocyanine Pigment A-5)
Equation (6)

(Miniaturized pigment (A-6))
Phthalocyanine pigment C.I. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and finely. A chemical pigment (A-6) was obtained.

(Miniaturized pigment (A-7))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of molecular sieve-dehydrated tert-amyl alcohol and 140 parts of sodium-tert-amyl alkoxide were added under a nitrogen atmosphere and heated to 100 ° C. with stirring to prepare an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and heated to 90 ° C. with stirring to dissolve them to prepare a solution of a mixture thereof. The heated solution of this mixture was slowly added dropwise to the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropping, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and the mixture was cooled to −10 ° C. This cooled mixture was cooled to 75 ° C. using a high-speed stirring disperser while rotating a share disk having a diameter of 8 cm at 4000 rpm, and the alkali metal salt of the previously obtained diketopyrrolopyrrole compound was obtained. The solution was added in small portions. At this time, the rate at which the alkali metal salt of the diketopyrrolopyrrole compound is added at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid, and water is always maintained at −5 ° C. or lower. Was added in small portions over approximately 120 minutes while adjusting. After the addition of the alkali metal salt, red crystals were precipitated and a red suspension was formed. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to prepare a suspension having a methanol concentration of about 90%, and the paste was stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the water paste of the obtained diketopyrrolopyrrole compound was filtered by an ultrafilter, dried at 80 ° C. for 24 hours, and pulverized to obtain diketopyrrolopyrrole pigment 1.
Next, 100 parts of diketopyrrolopyrrole pigment 1, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. Next, the kneaded mixture was put into warm water and stirred for 1 hour while heating at about 80 ° C. to form a slurry, which was filtered and washed with water to remove salt and diethylene glycol, then dried at 80 ° C. for 24 hours and pulverized. A fine pigment (A-7) having a diketopyrrolopyrrole pigment was obtained.

(Refined pigment (A-8))
Copper phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Color Co., Ltd.), 1000 parts of crushed salt, and 100 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. did. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain a finely divided pigment (A-8).

(Miniaturized pigments (A-9 to 11))
Miniaturized pigments (A-9 to 11) of the quinophthalone pigments of the following formulas (7) to (9) were prepared according to the examples of JP2012-226110A. The structure is shown below.

(Miniaturized quinophthalone yellow pigment A-9)
Equation (7)

(Miniaturized quinophthalone yellow pigment A-10)
Equation (8)

(Miniaturized quinophthalone yellow pigment A-11)
Equation (9)

(Miniaturized pigment (A-12))
C. I. 100 parts of Pigment Yellow 138 (PY138) (BASF's "Pariotor Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 6 hours at 80 ° C. Kneaded. This mixture was put into 2000 parts of warm water and stirred for 1 hour while heating at 80 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove salt and solvent, and then dried at 80 ° C. for 24 hours to make a fine pigment (fine pigment). A-12) was obtained.

(Miniaturized pigment (A-13))
Isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (BASF's "Irgafore Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader and kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. The mixture was dried at ° C. for one day and night to obtain a finely divided pigment (A-13).

(Miniaturized pigment (A-14))
100 parts of metal complex yellow pigment (CI pigment yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 60 ° C. for 10 hours. Next, this mixture was put into 3 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and solvent, and then 80. It was dried at ° C. for one day and night to obtain a fine pigment (A-14).

(Miniaturized pigment (A-15))
Yellow pigment C.I. I. Pigment Yellow 185 (BASF's "Pariotol Yellow D1155"): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1-gallon kneader and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , A micronized pigment (A-15) was obtained.

<Dye manufacturing method>
(Resin 1 having a cationic group in the side chain)
67.3 parts of methyl ethyl ketone was placed in a 4-port separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis (2,4-dimethylvaleronitrile) ) Was made uniform in 6.5 parts and 25.1 parts of methyl ethyl ketone, charged in a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50 ° C. for 2 hours, then heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin 1 having a cationic group in the side chain having a resin component of 47% by mass of an ammonium group was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Dye 01 (AR52-JK))
Follow the procedure below to C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound composed of Acid Red 52 and a resin 1 having a cationic group in the side chain, was produced.
Resin 1 having a cationic group was added to 2000 parts of water in terms of non-volatile content in 30 parts of the side chain, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and the solution was added dropwise to the resin solution. After the dropping, the mixture was stirred at 60 ° C. for 120 minutes to carry out a sufficient reaction. To confirm the end point of the reaction, it was judged that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 32 parts of C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound of Acid Red 52 and a resin 1 having a cationic group in the side chain, was obtained. At this time, C.I. in Dye 01 (AR52-JK). I. The content of the active pigment component derived from Acid Red 52 was 25% by mass.

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

<Dye derivative (a1)>
The following dye derivative (a1-1) and dye derivative (a1-2) are mixed in the same amount and mixed.
It was used.
Dye derivative (a1-1)

Pc represents the phthalocyanine skeleton.

Dye derivative (a1-2)

(Production of Dispersant (a2) Solution)
A reaction vessel equipped with a gas introduction tube, a temperature, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed by solid content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were added as a catalyst, and the mixture was reacted at 100 ° C. for 7 hours. .. It was confirmed by measuring the acid value that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and PGMAc was added and diluted so that the solid content was 30% by measuring the solid content, and the acid value was 70 mgKOH / g. , A dispersant (a2) solution having a weight average molecular weight of 8500 was obtained.

<Production example of binder resin (B) liquid>
<Manufacturing of binder resin (B1-M: non-photosensitive resin) mixture>
(Preparation of binder resin (B1-1) solution)
196 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, and the temperature was raised to 80 ° C. After that, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) from the dropping tube. A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% in the previously synthesized resin solution. Acetate was added to prepare a binder resin (B1-1) solution. The mass average molecular weight (Mw) was 26000.

(Preparation of binder resin (B1-2) solution)
The inside of the flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was made into a nitrogen atmosphere, 210 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100 ° C. while stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate, and further 2,2'-azobisisobuty was dissolved. A solution prepared by dissolving 3.6 parts of ronitrile was added dropwise to a flask, and stirring was continued at 100 ° C. for 5 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% in the previously synthesized resin solution. Acetate was added to prepare a binder resin to obtain a resin (B1-2) solution having a mass average molecular weight (Mw) of 10000.

<Solvent (N)>
(N-1) Cyclohexanone 20 parts (N-2) Ethyl 3-ethoxypropionate 20 parts (N-3) Propylene glycol Monomethyl ether 20 parts (N-4) Cyclohexanol acetate 20 parts (N-5) Diproprene glycol 20 parts (N-1) to (N-5) of methyl ether acetate were mixed in the above mass parts to prepare a solvent (N).

<Preparation of coloring composition>
(Manufacturing of coloring composition)
[Manufacturing Example 1]
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then the pore diameter is 5. The mixture was filtered through a 0 μm filter to prepare a colored composition (X-1) having a non-volatile component of 20% by mass.
Pigment (A-1) 15.0 parts Pigment (A-9) 5.0 parts Dye derivative (a1) 1.5 parts Dispersant (a2: Non-volatile content 30% liquid) 5.0 parts Binder resin (B1-M) : Non-volatile content 20.0% liquid) 20.0 parts Binder (N) 53.5 parts

[Production Examples 2 to 14]
(Manufacturing of coloring compositions (X-2 to 14))
Coloring compositions (X-2 to 14) were prepared in the same manner as the coloring composition (X-1) except that the composition was changed to that shown in Table 1.

(Preparation of binder resin (B1-M) solution)
The same amount of the binder resin (B1-1) solution and the binder resin (B1-2) solution were mixed and stirred to prepare a binder resin (B1-M) mixture.

<Production example of binder resin (B2: photosensitive resin) mixture>
(Preparation of binder resin (B2-1) solution)
207 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, and the temperature was raised to 80 ° C. to replace the inside of the reaction vessel with nitrogen. After that, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2 from the dropping tube. A mixture of 1.33 parts of'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Carens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content is 20% in the previously synthesized resin solution. Acetate was added to prepare a binder resin (B2-1). The mass average molecular weight (Mw) was 18,000.

(Preparation of binder resin (B2-2) solution)
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the non-volatile acid value reached 1 mgKOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution having an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized photosensitive transparent resin solution. As described above, a binder resin (B2-2) solution was prepared by adding propylene glycol monomethyl ether acetate. The mass average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (B2-3) liquid)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 136 g of propylene glycol monomethyl ether acetate was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized photosensitive transparent resin solution. As described above, a binder resin (B2-3) solution was prepared by adding propylene glycol monomethyl ether acetate. The mass average molecular weight (Mw) was 13,000.

(Preparation of binder resin (B2-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate and 40 parts of methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Yushi), and 40 parts of propylene glycol monomethyl ether acetate, and prepare a chain transfer agent. As a dropping tank, 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate were well stirred and mixed.
395 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. It was. After that, 150 parts of propylene glycol monomethyl ether acetate was added and cooled 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. Propylene glycol monomethyl ether acetate was added so as to have a concentration of 20% by mass to obtain a binder resin (B2-4) solution. The mass average molecular weight (Mw) of the resin was 18,000, and the acid value per non-volatile component was 2 mgKOH / g.

(Preparation of binder resin (B2-M) mixture)
Four kinds of binder resin (B2-1) to (B2-4) liquids were mixed and stirred in the same amount to prepare a binder resin (B2-M) mixed liquid.

<Thermosetting compound (BE)>
-Epoxy compound (BE-1)
(BE-1-1) 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol
[EHPE-3150 (manufactured by Daicel)],
(BE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(BE-1-3) Trichloroisocyanuric acid triglycidyl (BE-1-1) to (BE-1--3) were mixed in equal amounts to prepare an epoxy compound (BE-1).
-Oxetane compound (BE-2):
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

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

(C-5) Pentaerythritol triacrylate (432 g, hexamethylene diisocyanate 84 g) was charged into a reaction vessel having a polyfunctional urethane acrylate content of 1 liter and 5 mouths according to the following, and reacted at 60 ° C. for 8 hours to obtain a (meth) acryloyl group. A product containing polyfunctional urethane acrylate (C-5) having the above was obtained. The proportion of polyfunctional urethane acrylate (C-5) in the product was 70% by mass, and the balance was other photopolymerizable. It is occupied by monomer. It was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(C-6) Bifunctional bisphenol A type (meth) acrylate
[ABE-300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
(C-7) Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
As described above, (C-1) to (C-7) were mixed in the same amount to obtain a polymerizable compound (C).

<Photopolymerization initiator (D)>
(D-1) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(D-2) 2- (Dimethylamino) -2-[(4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(D-4) 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
(D-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(D-6) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan Ltd.)]
(D-7) 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(D-8) Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
As described above, (D-1) to (D-8) were mixed in equal amounts to prepare a photopolymerization initiator (D).

<Thiol compound (E)>
(E1-1) Pentaerythritol tetrakis (3-mercaptobutyrate)
(E1-2) 1,3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (E1-3) Tri Methylolpropane tris (3-mercaptobutyrate)
(E1-4) 1,4-bis (3-mercaptobutylyloxy) butane (E2-1) trimethylolpropane tris (3-mercaptopropionate)
(E2-2) Pentaerythritol tripropanethiol

<Manufacturing of leveling agent (F) liquid>
(Manufacturing of leveling agent (FD-1-1) liquid)
117 parts by mass of methyl ethyl ketone, 50 parts by mass of 2-propanol, 4.69 parts by mass of 2,2'-bipyridyl, and 1.49 parts by mass of cuprous chloride were charged in a nitrogen-substituted reaction vessel, and the mixture was stirred at 20 ° C. for 30 minutes. .. Then, 78.1 parts by mass of 2-hydroxyethyl methacrylate and 2.93 parts by mass of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 20 ° C. for 16 hours under a nitrogen stream. Next, 45.8 parts by mass of methyl ethyl ketone, 19.5 parts by mass of 2-propanol, and 40 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate represented by the following formula are added, and the temperature is raised to 60 ° C. for 8 hours. It was. Further, 91.6 parts by mass of methyl ethyl ketone, 39 parts by mass of 2-propanol and 80 parts by mass of 2- (nonafluorobutyl) ethyl methacrylate were added and reacted for 26 hours. This reaction mixture was dissolved in methanol and reprecipitated with water / methanol to obtain a block polymer. 60 parts by mass of this block polymer is dissolved in 80 parts by mass of methyl ethyl ketone, 10 parts by mass of a tin 2-ethylhexanoate solution (0.2 mass% methyl ethyl ketone solution), and 0.1 parts by mass of a polymerization inhibitor (p-methoxyphenol). The temperature was raised to 60 ° C. by adding a portion. While introducing dry air into the solution, 44.1 parts by mass of a 50 mass% methyl ethyl ketone solution of 2-acryloyloxyethyl isocyanate was added dropwise, reacted for 1 hour, and further reacted at 80 ° C. for 3 hours to have a fluorine content of 20 mass. A solution of a fluorine-containing radical polymerizable copolymer, which is a% block copolymer, was obtained. Further, propylene glycol monomethyl ether acetate was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluororadical polymerizable copolymer.

(Manufacturing of leveling agent (FD-2-1-12) liquid)
Using methylisobutylketone as a solvent and t-butylperoxy-2-ethylhexarate as a polymerization initiator, polymerization is carried out on the side chain or poly (perfluoroalkylene ether) chain having a fluorinated alkyl group shown in Table 1 and its terminal. A polymerization reaction was carried out using a compound having a sex unsaturated group and a polymerizable unsaturated monomer having an adamantyl group having a reactive functional group to obtain a fluorine-containing resin solution.
After cooling to room temperature, about 2 g of the fluororesin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content in the fluororesin solution is 20% by weight. Acetate was added to obtain FDs 2-1 to 12 shown in Table 2.

FD1 and FD2 in Table 2 are shown below.

"-PFPE-" in the following formula represents a poly (perfluoroalkylene ether) chain.

<Sensitizer (G)>
(G-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(G-2) 4,4'-Bis (diethylamino) benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (G-1) and (G-2) were mixed in the same amount to prepare a sensitizer (G).

<Polymerization inhibitor (H)>
(H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) tert-Butylhydroquinone or more, (H-1) to (H-3) are mixed in equal amounts, and a polymerization inhibitor is added. It was designated as (H).

<Ultraviolet absorber (I)>
(I-1) 2- [4-[(2-Hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-Triazine [TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol [TINUVIN900 (manufactured by BASF Japan Ltd.)]
As described above, (I-1) and (I-2) were mixed in the same amount to prepare the ultraviolet absorber (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (J-2) 3,3'-dioctadecylthiodipropanoate (J-3) tris [2] , 4-Di- (tert) -butylphenyl] phosphine (J-4) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate or higher, (J) -1) to (J-5) were mixed in equal amounts to prepare an antioxidant (J).

<Storage stabilizer>
(L-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (L-1) and (L-2) were mixed in equal amounts to prepare a storage stabilizer.

<Adhesion improver>
(M-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (M-1) to (M-4) were mixed in the same amount to prepare an adhesion improver.

<Manufacturing method of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (X-1: non-volatile content 27.0%): 50.0 parts binder resin (B2-M: non-volatile content 20.0%): 15.0 parts thermosetting compound (BE-1): 1 .0 parts thermosetting compound (BE-2): 1.0 part polymerizable compound (C): 3.0 parts photopolymerization initiator (D): 1.8 parts thiol compound (E1-1): 0 .4 parts Fluorine-based surfactant (FD-2-1: Non-volatile content 3%): 1.0 parts Sensitizer (G): 0.2 parts Polymerization inhibitor (H): 0.1 parts Ultraviolet absorber (I): 0.1 part Antioxidant (J): 0.1 part Storage stabilizer (L): 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 26.0 Department

[Examples 2-52, Comparative Examples 1-6]
(Preparation of Photosensitive Coloring Compositions (Y-2 to 58))
Photosensitive coloring compositions (Y-2 to 58) were prepared in the same manner as in Example 1 except that the types of the coloring composition and the binder resin solution of Example 1 were changed as shown in Table 3.
The raw materials for each are as described above.

<Evaluation of photosensitive coloring composition>
Each test was performed by the following method. The test results are shown in Table 4.
The meaning of the evaluation rank is as follows.
◎: Extremely good 〇: Good △: Practical use ×: Not suitable for practical use

(Pattern shape evaluation)
The obtained photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 0.7 mm so as to have a film thickness of 3.4 μm, and passed through a mask having a stripe pattern having a width of 100 μm under the condition of 40 mJ / cm ² . UV exposure was performed at. Then, a pattern is obtained by immersing in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 40 seconds for development, and washing with pure water. It was. The obtained coating film was heat-treated (post-baked) in an oven at 230 ° C. for 20 minutes, and the pattern shape was confirmed with a scanning electron microscope (“S-3000H” manufactured by Hitachi High-Tech Co., Ltd.). For the evaluation, an SEM image of a cross section of a striped pattern having a width of 100 μm was captured, and the taper angle between the base material and the end of the pattern cross section was evaluated using a protractor as follows.

⊚: Taper angle 50 degrees or more and less than 90 degrees 〇: 40 to less than 50 degrees Δ: 30 to less than 40 degrees
×: Less than 30 degrees

(Water stain evaluation)
Similar to the pattern shape evaluation described above, a substrate having both a patterned portion and a non-patterned portion was prepared, and water stains on the solid coated portion without a pattern were observed with a magnifying glass. The evaluation criteria are as follows.
⊚: There was no water stain.
〇: Water stain was less than 10% of the solid part.
Δ: Water stain was 10% or more and less than 30% of the solid portion.
X: Water stain was 30% or more of the solid portion.

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 Orientation layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (6)

A photosensitive coloring composition containing a colorant (A), a polymerizable compound (B), a binder resin (C), a photopolymerization initiator (D), a thiol compound (E), and a fluorine-based leveling agent (F). The photosensitive coloring composition is characterized in that the thiol-based compound (E) contains the thiol-based compound (E1) represented by the following general formula (1).
General formula (1)
(In the general formula (1), R is an n-valent organic group, and n is an integer of 1 to 4.) The fluorinated leveling agent (F) is an ethylenically unsaturated monomer (FD1) containing an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain, and another ethylenically unsaturated monomer (FD2). ) And a copolymer (FD) of the above, according to claim 1. The photosensitive coloring composition. According to any one of claims 1 or 2, the thiol compound (E1) represented by the general formula (1) is contained in an amount of 0.1 to 7.5% by mass based on the total non-volatile content of the coloring composition. The photosensitive coloring composition according to the above. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the thiol-based compound (E) contains a thiol-based compound (E2) other than the thiol-based compound (E1). A color filter comprising a base material and a filter segment formed by using the photosensitive coloring composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5.