JP2021051119A - Photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Abstract

To provide a photosensitive coloring composition which can form a film excellent in a pattern shape and adhesion regardless of a large content of a coloring agent, and can shorten development time (high development speed).SOLUTION: A photosensitive coloring composition contains a coloring agent (A), a binder resin (B), a polymerizable compound (C) and a photopolymerization initiator (D). The coloring agent (A) is contained in an amount of 40-70 mass% in 100 mass% of a non-volatile content of the photosensitive coloring composition. The binder resin (B) contains a photosensitive resin (B1) having an acid value of 100-300 mgKOH/g and a weight average molecular weight of 2,000-20,000, and the polymerizable compound (C) contains an alicyclic compound (C-1) having two polymerizable unsaturated groups.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive coloring composition used for a color liquid crystal display device, a color solid-state image sensor, an organic EL display device, a quantum dot display device, a color filter such as electronic paper, and the like.

Color liquid crystal displays (hereinafter referred to as LCDs) are required to further improve their color reproduction characteristics. Therefore, the photosensitive coloring composition used for forming the color filter has been dealt with by increasing the content of the colorant and increasing the thickness of the coating film. However, when the content of the colorant is increased, there are problems that the light sensitivity is lowered, the developability and the resolvability are deteriorated. Further, when the thickness of the coating film is increased, it is difficult for light to reach the deepest part of the coating film, and there is a problem that the shape of the resist pattern is deteriorated due to poor curability.

Therefore, in Patent Document 1 and Patent Document 2, (1) the use of a photocurable binder resin, (2) an increase in the amount of a photopolymerization initiator and a sensitizer, and (3) optimization of the type and amount of the polymerizable compound. Was being done.

Japanese Unexamined Patent Publication No. 2001-264530 Japanese Unexamined Patent Publication No. 2003-156842

However, in the conventional photosensitive coloring composition, when the amount of the photopolymerization initiator is increased, coloring derived from the photopolymerization initiator and deterioration of heat resistance occur. Further, as the amount of the colorant was increased, the light transmittance was reduced, so that the adhesion of the coating film after curing was lowered, and the deterioration of the shape of the pattern could not be eliminated. In addition, increasing the amount of the polymerizable compound caused a problem of tack on the film.

INDUSTRIAL APPLICABILITY The present invention is a photosensitive coloring composition capable of forming a film having excellent pattern shape and adhesion to a large amount of a colorant and shortening a developing time (fast developing speed). For the purpose of providing.

The photosensitive coloring composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
40 to 70% by mass of the colorant (A) is contained in 100% by mass of the non-volatile content of the photosensitive coloring composition.
The binder resin (B) contains a photosensitive resin (B1) having an acid value of 100 to 300 mgKOH / g and a weight average molecular weight of 2,000 to 20,000.
The polymerizable compound (C) contains an alicyclic compound (C-1) having two polymerizable unsaturated groups.

According to the above invention, in spite of the high content of the colorant, in addition to being able to form a film having excellent pattern shape and adhesion, the development time can be shortened (development speed is high) and the photosensitive property. Coloring compositions and color filters can be provided.

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

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. The polymerizable unsaturated group is an ethylenically unsaturated group, and examples thereof include a vinyl group and a (meth) acryloyl group. The monomer is a polymerizable unsaturated group-containing compound. The filter segment is also called a pixel.

The photosensitive coloring composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
40 to 70% by mass of the colorant (A) is contained in 100% by mass of the non-volatile content of the photosensitive coloring composition.
The binder resin (B) contains a photosensitive resin (B1) having an acid value of 100 to 300 mgKOH / g and a weight average molecular weight of 2,000 to 20,000.
The polymerizable compound (C) contains an alicyclic compound (C-1) having two polymerizable unsaturated groups.

The photosensitive coloring composition of the present invention is preferably used for forming an arbitrary pattern by a photolithography method on a coating film formed by coating. Examples of the application include a color filter application such as an LCD color solid-state image sensor, an organic EL display device, a quantum dot display device, and electronic paper. Needless to say, the present invention is not limited to the above-mentioned applications.

<Colorant (A)>
The colorant (A) contains a pigment and a dye. Examples of pigments include organic pigments and inorganic pigments. 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. Hereinafter, specific examples of organic pigments are shown by color index numbers.

Red pigments include, for example, 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. 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, preferably C.I. I. Pigment Red 177, 254, 291, 295, 296 are more preferred.

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 can be used in combination.

The blue pigment is, for example, 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 is preferred. I. Pigment Blue 15: 6 is more preferred. Further, the purple pigment described later can be used in combination with the blue coloring composition.

Purple pigments include, for example, 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, Examples thereof include 37, 39, 42, 44, 47, 49 and 50. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23 is preferred, C.I. I. Pigment Violet 23 is more preferred.

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, Pigments described in 192, 193, 194, 196, 198, 199, 213, 214, and Japanese Patent Application Laid-Open No. 2012-226110 can be used.
Preferably C.I. I. Pigment Yellow 138, 139, 150, 185 The pigments described in JP2012-226110A can be used.

Examples of the cyan coloring composition for forming the cyan filter segment include 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.

The green pigment is, for example, 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, Aluminum Phthalocyanine Pigment (A1) can be mentioned. Among these, 36, 58, 59, aluminum phthalocyanine pigment (A1) is preferable, and aluminum phthalocyanine pigment (A1) is more preferable.

<Aluminum phthalocyanine pigment (A1)>
As used herein, the colorant (A) preferably contains an aluminum phthalocyanine pigment (A1).
The aluminum phthalocyanine pigment (A1) is, for example, a known pigment described in JP-A-2017-11138. In the present specification, by using the aluminum phthalocyanine pigment (A1), a color filter having good optical characteristics can be formed.

<Pigment miniaturization>
When the colorant (A) is an organic pigment, 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. The appropriate particle size further improves the dispersibility and the contrast ratio of the coating film. The average primary particle size 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.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mixed, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like in a batch or continuous manner. This is a treatment 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 formula 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, inexpensive sodium chloride (salt) is preferable. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, more preferably 300 to 1000% by mass, based on 100% by mass of the pigment.

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 in terms of being less likely 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.

When the pigment is salt milled, it is resinated as needed. Examples of the resin include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. The resin is preferably solid at room temperature (25 ° C.) and water insoluble. It is also preferable that the resin is partially soluble in an organic solvent depending on the embodiment. The amount of the resin used is preferably 5 to 200% by mass with respect to 100% by mass of the pigment.

Inorganic pigments include, for example, 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, amber, etc. Synthetic iron black and the like can be mentioned. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

<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.

Dyes include, for example, azo dyes, disazo dyes, azomethine dyes (Indian aniline dyes, Indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthra). Pyridone dyes, etc.), Carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes, etc. Dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo Examples thereof include 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. It is described in.

The colorant (A) can be used alone or in combination of two or more.

<Dye derivative>
As the photosensitive coloring composition, a dye derivative can be used 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 phosphoric acid 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, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Diketopyrrolopyrrole dye derivatives are JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, and phthalocyanine dye derivatives are special. Kai 2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, Patent No. 5735266, and anthraquinone-based dye derivatives are JP-A-63-264674, 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. No., JP-A-2000-273383, Dioxazine-based dye derivative is JP-A-2011-162662, Thiadine-indigo-based dye derivative is JP-A-2007-314785, Triazine-based dye derivative 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 For dye derivatives, JP-A-2009-57478, for quinophthalone-based dye derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, Naphthol-based dye derivatives are JP-A-2012-208329, JP-A-2014-5439, azo-based dye derivatives are JP-A-2001-172520, JP-A-2012-1722092, and acidic substituents are special. Kai 2004-307854 and basic substituents are dye derivatives described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. Can be mentioned. 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, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

The amount of the dye derivative used is preferably 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 a pigment and performing pigmentation treatments such as acid pacing, acid slurry, dry milling, salt milling, and solven salt milling, the pigment derivative is adsorbed on the pigment surface and no dye derivative is added. The primary particles of the pigment can be made finer than in the case.

By adding a dye derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the dye derivative is adsorbed on the pigment surface. As a result, the surface of the pigment has a polarity, which promotes the adsorption of the resin-type dispersant, so that the compatibility of the pigment, the binder resin (B), the polymerizable compound (C), the photopolymerization initiator (D), etc. becomes It is improved, and the dispersion stability and the aging stability of the photosensitive coloring composition are improved. Further, by improving the compatibility, the coating film is excellent in stability over time when the photosensitive coloring composition is applied to a glass substrate or the like, and the waiting time from application to exposure of the photosensitive coloring composition (PCD: Post Coating). Stability and characteristic dependence such as pattern shape with respect to delay) and waiting time from exposure to heat treatment (PED: Post Exposure Delay), and 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 can be suppressed.

<Resin type dispersant>
The photosensitive coloring composition may contain a resin-type dispersant. The resin-type dispersant has a colorant-affinity portion that adsorbs to the colorant (A) and a relaxation portion that has a high affinity for components other than the colorant and causes the colorant (A) dispersed particles to repel each other in three dimensions.
Resin-type dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, ammonium polycarboxylic acid salts, and polycarboxylic acids. It was formed by the reaction of acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products of these, poly (lower alkyleneimine), with polyesters having free carboxy groups. Oily dispersants such as amides and salts thereof, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, Examples thereof include water-soluble resins such as polyvinylpyrrolidone, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.
Further, the polymer dispersant having a basic functional group contains a nitrogen atom having a nitrogen atom-containing graft copolymer, 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 amount of the resin-type dispersant used is preferably about 3 to 200% by mass, more preferably 5 to 100% by mass, based on the colorant (A). When an appropriate amount is used, the film forming property is further improved.

<Binder resin (B)>
The binder resin (B) 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 (B) includes, for example, a thermoplastic resin using thermal energy and a thermosetting resin. These resins may be an active energy ray-curable resin having a polymerizable unsaturated group and being cured by an active energy ray, or a resin having no polymerizable unsaturated group.

The binder resin (B) contains a photosensitive resin (B1) having an acid value of 100 to 300 mgKOH / g and a weight average molecular weight of 2,000 to 20,000. By having an appropriate acid value, it is possible to achieve both alkaline developability and a pattern shape with good linearity at a high level. Further, by having an appropriate Mw, it is possible to achieve both adhesion to a base material (substrate) and alkali developability at a high level. The acid value is more preferably 100 to 200 mgKOH / g. The Mw is preferably 3,000 to 15,000. The value of Mw (weight average molecular weight) / Mn (number average molecular weight) is preferably 10 or less.

Further, the photosensitive resin (B1) preferably contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in the side chain selected from the following (I) and (II). By having photosensitivity, the coating film is three-dimensionally crosslinked to increase the crosslink density and improve chemical resistance.
(I) An alkali-soluble resin obtained by reacting a product of an epoxy group in an epoxy group-containing resin with a carboxy group-containing monomer with a polybasic acid anhydride.
(II) An alkali-soluble resin which is a reaction product of a carboxy group in a carboxy group-containing resin and an epoxy group-containing monomer.

The blending amount of the binder resin (B) is preferably 2 to 80 parts by mass, more preferably 10 to 60 parts by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

<Photosensitive resin (B1) of (I)>
The photosensitive resin (B1) of (I) can be synthesized by a method of reacting a polybasic acid anhydride with a hydroxyl group generated by a reaction between an epoxy group contained in the resin and a carboxy group-containing monomer.

Explaining the synthesis method of (I) in detail, for example, a carboxy group of a calciuml group-containing monomer is added to a side chain epoxy group of a resin obtained by copolymerizing an epoxy group-containing monomer and another monomer. Addition reaction. Next, a polymerizable unsaturated group and a carboxy group can be introduced by reacting the generated hydroxyl group with a polybasic acid anhydride.

Epoxy group-containing monomers include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3,4-. Epoxycyclohexyl (meth) acrylate can be mentioned. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with the carboxy group-containing monomer.

The carboxy group-containing monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted compound. Such as monocarboxylic acid and the like.

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 carboxy groups, a tricarboxylic dianhydride such as trimellitic dianhydride was used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride was used to remain. It is also possible to hydrolyze the anhydride group.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) (Meta) acrylates such as acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene glycol (meth) acrylate,
Also, (meth) acrylamide such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Styrene, styrenes such as α-methylstyrene, ethylvinyl ether, n-propylvinyl ether, isopropylvinyl ether, n-butylvinyl ether, vinyl ethers such as isobutylvinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate, etc. Can be mentioned.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidecoumarin. , 4,4'-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimoleimide, N, N'-1,4-phenyl Range maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzylmaleimide , N-Bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexa Noart, N- [4- (2-benzoimidazolyl) phenyl] maleimide, N-substituted maleimides such as 9-maleimideacrinedin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate , Eethyleneoxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

<Photosensitive resin (B1) of (II)>
The photosensitive resin (B1) of (II) can be synthesized by a method of reacting the carboxy group of the resin with the epoxy group-containing monomer.

Explaining the synthesis method of (II) in detail, for example, a single amount of epoxy group contained in a part of the side chain carboxy groups of the resin obtained by copolymerizing a carboxy group-containing monomer and other monomers. A polymerizable unsaturated group and a carboxy group can be introduced by an addition reaction of the body epoxy group. The raw materials used for the synthesis of the photosensitive resin (B1) of (II) are the same as those of (I) above.

<Binder resin (B) other than photosensitive resin (B1)>
As the binder resin (B), a resin other than the photosensitive resin (B1) (hereinafter, referred to as other resin) can be used in combination. Examples of other resins include an alkali-soluble resin having no polymerizable unsaturated group, an alkali-soluble resin having a polymerizable unsaturated group, and a thermoplastic resin having no alkali-soluble group.

Examples of the alkali-soluble resin having no polymerizable unsaturated group include resins having an acidic group such as a carboxy group and a sulfone group. The alkali-soluble resin having no polymerizable unsaturated group includes, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, and an ethylene / (meth) acrylic. Examples thereof include acid copolymers and isobutylene / (anhydrous) maleic acid copolymers. 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. By using these, the degree of curing of the coating film can be adjusted as appropriate.

The alkali-soluble resin having a polymerizable unsaturated group is preferably, for example, a resin that does not satisfy at least one of the acid value of the photosensitive resin (B1) and the weight average molecular weight. The alkali-soluble resin having a polymerizable unsaturated group can be synthesized, for example, by the synthesis method of (I) or the synthesis method of (II). Further, for example, it can also be synthesized by a method of reacting an isocyanate group of an isocyanate group-containing monomer with a side chain hydroxyl group of a resin obtained by copolymerizing a hydroxyl group-containing monomer and another monomer. Needless to say, the alkali-soluble resin having a polymerizable unsaturated group is not limited to the above-mentioned resin.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth). Examples thereof include hydroxyalkyl methacrylates such as acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to 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 isocyanate group-containing monomer include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate.

The other monomer is the same as the other monomer described above.

The thermoplastic resin having no alkali solubility is a resin other than the resins described so far. 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, polyester resin, vinyl Examples thereof include resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

<Thermosetting resin (E)>
The photosensitive coloring composition can further contain a thermosetting resin.
Examples of the thermosetting resin include epoxy resin, oxetane resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin. Among these, epoxy resin and oxetane resin are preferable, and epoxy resin (E1) is more preferable.

<Epoxy resin (E1)>
The epoxy resin (E1) includes, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene). , Alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymers of substances, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols Polycondensate of and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, Polycondensate with biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Polycondensate, polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, Examples thereof include glycidyl ester-based epoxy resins.

The thermosetting resin (E) can be used alone or in combination of two or more.

The blending amount of the thermosetting resin (E) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. This further improves heat resistance and resolution.

<Polymerizable compound (C)>
The polymerizable compound (C) includes an alicyclic compound (C-1) having two polymerizable unsaturated groups (hereinafter, referred to as an alicyclic compound (C-1)). As a result, the development speed is further improved.

<Alicyclic compound (C-1)>
Examples of the alicyclic compound (C-1) include monomers represented by the following general formula (1).

一般式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基を示し、Ｘは、ジシクロペンタニル構造又はジシクロペンテニル構造を有する２価の連結基を示し、Ｒ^３及びＲ^４は、それぞれ独立に炭素数１〜４のアルキレン基を示し、ｎ及びｍは、それぞれ独立に０〜２の整数を示し、ｐ及びｑはそれぞれ独立に０以上の整数を示し、ｐ＋ｑ＝０〜１０となるように選択される。

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X represents a divalent linking group having a dicyclopentanyl structure or a dicyclopentenyl structure, and R ³ And R ⁴ independently represent an alkylene group having 1 to 4 carbon atoms, n and m independently represent an integer of 0 to 2, p and q each independently represent an integer of 0 or more, and p + q. It is selected so that = 0 to 10.

In the above general formula (1), R ³ and R ⁴ are each independently preferably an ethylene group or a propylene group, and more preferably an ethylene group. Further, the propylene group may be either an n-isopropylene group or an isopropylene group.

In the above general formula (1), n and m are the average number of methylene groups added. p and q are the average number of alkoxy groups added. When p + q is 2 or more, two or more R ³ and R ⁴ may be the same or different.

In the monomer represented by the general formula (1), since the divalent linking group having the dicyclopentanyl structure or the dicyclopentenyl structure of X has a bulky structure, the hygroscopicity of the coating film is suppressed and the metal Corrosion of wiring and transparent electrodes can be greatly suppressed.

The dicyclopentanyl structure and the dicyclopentenyl structure can also be referred to as a tricyclodecane skeleton and a tricyclodecene skeleton, respectively. The "tricyclodecane skeleton" and the "tricyclodecene skeleton" refer to the following structures (each having an arbitrary bond).

Commercially available products of the monomer represented by the general formula (1) include, for example, tricyclodecanedimethanol dimethacrylate, DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name), tricyclodecanedimethanol diacrylate, and A-DCP. (Product name manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can be mentioned.

Other polymerizable compounds other than the monomer represented by the general formula (1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like. Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, Trimethylol Propane Tri (meth) Acrylate, Phenoxytetraethylene Glycol (Meta) Acrylate, Phenoxy Hexaethylene Glycol (Meta) Acrylate, Trimethylol Propane PO Modified Tri (Meta) Acrylate, Trimethylol Propane EO Modified Tri (Meta) 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- Hexadiol 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) Various acrylic acid esters such as acrylate, tricyclodecanyl (meth) acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane acrylate, and methacrylate ester, (meth) acrylic acid, styrene, acetic acid. Examples thereof include vinyl, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

The content of the alicyclic compound (C-1) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When it is contained in an appropriate amount, the developing speed is improved and a pattern having a good cross-sectional shape can be obtained.

(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 carboxy 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 carboxy group-containing monoesterides 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 carboxy group with monohydroxymonomethacrylates.

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

The hydroxyl group-containing (meth) acrylate includes, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

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 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 titanosen compounds. Among these, oxime ester compounds are preferable.

(Oxime ester compound)
When an oxime ester compound absorbs ultraviolet rays, the NO bond of the oxime is cleaved to generate an iminyl radical and an alkyroxy radical. 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. Ester-based photopolymerization initiators can be mentioned.

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

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 (A). When an appropriate amount is contained, the photocurability and developability are further improved.

<Sensitizer>
The photosensitive coloring composition may contain a sensitizer. The sensitizer includes, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives , Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylglioxylates, benzyls, 9,10-phenanthrene quinones, camphorquinones, ethyl anthraquinones, 4,4'-diethylisophthalofenones, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned. Among these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferable. Specific compounds include 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 and the like are preferable.

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, based on 100 parts by mass of the photopolymerization initiator (D). When an appropriate amount is contained, curability and developability are further improved.

<Thiol chain transfer agent>
The photosensitive coloring composition may contain a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, it functions as a chain transfer agent in the radical polymerization process after light irradiation, and the photosensitivity is improved by generating chile radicals that are less susceptible to polymerization inhibition by oxygen.

The thiol-based chain transfer agent is preferably a polyfunctional aliphatic thiol having two or more thiol groups and bonded to an aliphatic group such as methylene or ethylene. The thiol group is more preferably 4 or more. The thiol-based chain transfer agent improves the curability near the deepest part of the coating in proportion to the increase in the number of thiol groups.

Polyfunctional aliphatic thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopro. Pionate, Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propanetris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetraxthiopropionate, Trimercaptopropion Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s -Triazine and the like can be mentioned, and preferred examples include ethylene glycol bisthiopropionate, trimethylpropanthithiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the light sensitivity is improved, the tapered shape of the pixel is improved, and wrinkles are less likely to occur on the film surface.

<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.

Antipolymerization agents include, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl. Catecol, 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-tert Alkylcatechol compounds such as −butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-Di-tert-alkylhydroquinone compounds such as butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, phosphine compounds such as tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide and the like. Examples thereof include phosphite compounds such as phosphine oxide compounds, 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 (F)>
The photosensitive coloring composition can contain an ultraviolet absorber (F). The ultraviolet absorber (F) is a compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate ester compounds, cyanoacrylate compounds, and salicylate compounds. .. Among these, benzotriazole-based compounds are preferable in terms of obtaining a good pattern shape.

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

The total content of the photopolymerization initiator (D) and the ultraviolet absorber (F) 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.

The benzotriazole-based compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3. , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-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) -Dimethylethyl) -4-hydroxy, C7-9 side chain and mixture of 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) -(2H-benzotriazole-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 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- [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 mentioned.

The triazine compound is, for example, 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-dihydroxy) Phenyl) -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-( Hexyloxy) 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 mentioned.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 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, Examples thereof include 2,2', 4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be mentioned.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert butyl phenyl salicylate. Other examples include oligomer-type and polymer-type compounds having a salicylic acid ester structure.

<Antioxidant>
The photosensitive coloring composition may contain an antioxidant. When the antioxidant contains a photopolymerization initiator (D) or a thermosetting resin (E), the film can prevent yellowing due to oxidation in the thermal process during thermal curing or ITO annealing. As a result, the transmittance of the coating film can be improved.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film. In the present specification, the antioxidant is preferably a compound containing no halogen atom.

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

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

<Leveling agent>
The photosensitive coloring composition may contain a leveling agent. As a result, the coatability on the base material and the drying property of the coating film are improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

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

The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. It is possible to improve the coatability, adhesion, and transmittance contained in an appropriate amount in a well-balanced manner.

<Storage stabilizer>
The photosensitive coloring composition may contain a storage stabilizer. As a result, the change in viscosity with time can be suppressed. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite.

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

The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

<Adhesion improver>
The photosensitive coloring composition may contain a storage stabilizer. This improves the adhesion to the base material and makes it easier to obtain a narrow pattern shape. The adhesion improver is preferably a silane coupling agent or the like.

Adhesion improvers include, for example, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -(Meta) acrylic silanes such as methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, 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, 3-mercaptopropylmethyl Mercaptos such as dimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, and sulfides such as bis (triethoxysilylpropyl) tetrasulfide. Examples thereof include silane coupling agents such as isocyanates such as 3-isocyanoxide propyltriethoxysilane.

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

The content of the storage stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A). Adhesion, resolution, and sensitivity can be improved in a well-balanced manner by using an appropriate amount.

<Solvent>
The photosensitive coloring composition may contain a solvent. When forming a film for a color filter, it is used for adjusting the viscosity for forming a dry film having a thickness of about 0.2 to 5 μm.

The solvent is preferably an organic solvent, and can be arbitrarily selected in consideration of, for example, boiling point, SP value, evaporation rate, and viscosity.

Examples of the solvent include an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and an 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 (solvent containing OH in the molecule, -O −, −CO− and −COO− -free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like. Among these, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable in terms of coatability and dryness. For example, 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 preferable.

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

<Manufacturing method of photosensitive composition>
The photosensitive coloring composition is subjected to a dispersion treatment using, for example, a colorant (A), a dispersant, a solvent, or the like to prepare a colorant (A) dispersion. Next, it can be prepared by mixing a colorant (A) dispersion, a binder resin (B), a photopolymerizable compound (D), and a photopolymerizable initiator (E). When the colorant (A) can be dispersed more finely by using a dispersion aid such as a dye derivative in combination during the dispersion treatment, or when the colorant (A) has high solubility in a solvent such as a dye or an inorganic pigment, It may not require distributed processing. When two or more kinds of the colorant (A) are used in combination, the colorant (A) dispersion may use the colorant (A) separately, or a plurality of colorants (A) may be used in combination. Needless to say, the timing of blending each material is arbitrary.

For the dispersion treatment, for example, a disperser such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor can be used.

The composition of the photosensitive coloring composition can be arbitrarily adjusted by a known method so that it can be applied to a photolithography method. Examples of the photolithography method include solvent development type and alkali development type.

<Removal of coarse particles>
As for the photosensitive coloring composition, it is preferable in the present specification to remove the coarse particles contained therein after the step of the colorant (A) dispersion or the preparation of the photosensitive coloring composition. As a result, foreign matter can be removed from the coating film, so that a fine pattern can be easily formed.
The removal is preferably performed by, for example, a method such as centrifugation, a sintering filter, or a membrane filter. As a result, foreign matter such as coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles can be removed. As described above, the photosensitive coloring composition preferably contains substantially no particles of 0.5 μm or more, and preferably does not contain 0.3 μm or less.

<Color filter>
As used herein, a color filter comprises a substrate (also referred to as a transparent substrate) and a filter segment formed from a photosensitive coloring composition. The color filter segment (hereinafter, also referred to as a filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of the colorant (A) to be used. Further, the color filter may have a magenta color filter segment, a cyan color filter segment, and a yellow filter segment instead of the filter segment. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate that uses an aluminum electrode or a metal thin film as a reflective surface.

<Manufacturing method of color filter>
It is preferable that the color filter first forms a black matrix on the base material 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.
Since the printing method can form a pattern only by repeating printing and drying of the photosensitive coloring composition prepared as a printing ink, it is low cost and excellent in mass productivity as a manufacturing method of a color filter. 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 color filter is produced by electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the transparent substrate. 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 does not come into 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 present specification, after the filter segment is formed, the color filter is bonded to the facing substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and polarization is performed as necessary. A liquid crystal display device can be manufactured by laminating a film or a retardation film on the outside of a substrate. This liquid crystal display device is, for example, twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convensend bend ( OCB) and the like.

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>
The liquid crystal display device of the present specification includes a color filter.
The liquid crystal display device 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 in that 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. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments 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. 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, but the present invention is not limited thereto. In Production Examples and Examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

Hereinafter, a method for measuring the physical property value 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 ° C. , THF solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. 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 Co., Ltd.) ) Was titrated, and the acid value (mgKOH / g) of the resin solution was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile component concentration of the resin solution.

(Miniaturized pigments (A1-1) to (A1-5)
The finely divided pigments (A1-1) to (A1-5) of the following chemical formulas (51) to (55) were prepared according to the examples of JP-A-2017-11138.

(Miniaturized pigments (A-6) to (A-8))
Miniaturized pigments (A-6) to (A-8) of quinophthalone pigments represented by the following chemical formulas (56) to (58) were prepared according to the examples of JP2012-226110A. The structure is shown below.

(Miniaturized pigment (A-9))
Kinoftalone yellow pigment C.I. I. 100 parts of Pigment Yellow 138 (PY138) (BASF Japan'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) and 6 at 80 ° C. Time kneaded. This mixture was poured into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours and 95 parts. A micronized pigment (A-9) was obtained.

(Refined pigment (A-10))
Isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (“Irgafore Yellow 2R-CF” manufactured by BASF Japan Ltd.), 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 warm water of 3 liters, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, and after repeating filtration and washing with water to remove sodium chloride and solvent. , 80 ° C. for one day and night to obtain a finely divided pigment (A-10).

(Miniaturized pigment (A-11))
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 warm water of 3 liters, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, and after repeating filtration and washing with water to remove sodium chloride and solvent. , 80 ° C. for one day and night to obtain a finely divided pigment (A-11). The average primary particle size was 36.6 nm.

(Miniaturized pigment (A-12))
Isoindoline yellow pigment C.I. I. Pigment Yellow 185 (“Pariotol Yellow D1155” manufactured by BASF Japan Ltd.): 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 warm water of 5 liters, 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. Then, a refined pigment (A-12) was obtained.

<Dye derivative (b0)>
Dye derivative (b0-1)

<Manufacturing of resin type dispersant>
(Manufacturing of resin type dispersant solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of propylene glycol monomethyl ether acetate, 0.1 part of dimethylbenzylamine was charged. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of ETERNALCOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Kosan Co., Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, propylene glycol monomethyl ether acetate. Ten parts were charged, and 0.2 part of 2,2'-azobisisobutyronitrile was added every 30 minutes in 15 portions while keeping the inside of the reaction vessel at 80 ° C. The non-volatile content was measured 1 hour after the final addition color, and a coat in which 95% of the monomers had reacted was confirmed. A resin mold having a carboxy group having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000 after diluting with propylene glycol monomethyl ether acetate so that the non-volatile content is 20% in the non-volatile content measurement. A dispersant solution was obtained.

<Preparation of binder resin (B) solution>
(Preparation of binder resin (B-1) solution)
100 parts of PGMEA 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, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then the dropping tube. A mixture of 50 parts of benzyl methacrylate, 12 parts of methacrylic acid, 20 parts of methyl methacrylate, and 1.5 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, 1.0 part of 2,2'-azobisisobutyronitrile dissolved in 40 parts of propylene glycol monomethyl ether acetate was added, and then stirring was continued at the same temperature for 3 hours to carry out copolymerization. Obtained coalescence. After cooling to room temperature, PGMEA was added so that the non-volatile content was 40% by mass to prepare a binder resin (B-1) solution having no polymerizable unsaturated group. The binder resin (B-1) had a non-volatile acid value of 95 mgKOH / g and a mass average molecular weight (Mw) of 9,000.

(Preparation of photosensitive resin (B-2))
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 [0.50 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 resin solution. After cooling to room temperature, about 2 g of the photosensitive resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by mass in the previously synthesized photosensitive resin solution. A photosensitive resin (B-2) solution was prepared by adding propylene glycol monomethyl ether acetate. The binder resin (B-2) had a non-volatile acid value of 80 mgKOH / g and a mass average molecular weight (Mw) of 12,000.

(Preparation of photosensitive resin (B1-1))
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. 52.9 g (0.30 mol) of benzyl methacrylate, 85.3 g (0.60 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 51.7 g of methacrylic acid [0.60 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, 55.0 g (0.55 mol) of succinic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive resin solution. After cooling to room temperature, about 2 g of the photosensitive resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by mass in the previously synthesized photosensitive resin solution. A photosensitive resin (B1-1) solution was prepared by adding propylene glycol monomethyl ether acetate. The binder resin (B1-1) had a non-volatile acid value of 112 mgKOH / g and a mass average molecular weight (Mw) of 12,000.

(Preparation of photosensitive resin (B1-2))
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. 17.6 g (0.10 mol) of benzyl methacrylate, 120.8 g (0.85 mol) of glycidyl methacrylate, 11.0 g (0.05 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 73.2 g of methacrylic acid [0.85 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, 80.0 g (0.80 mol) of succinic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive resin solution. After cooling to room temperature, about 2 g of the photosensitive resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by mass in the previously synthesized photosensitive resin solution. A photosensitive resin (B1-2) solution was prepared by adding propylene glycol monomethyl ether acetate. The binder resin (B1-2) had a non-volatile acid value of 145 mgKOH / g and a mass average molecular weight (Mw) of 12,000.

(Adjustment of photosensitive resin (B1-3) 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 14.2 g of glycidyl methacrylate [0.10 mol, (20 mol% with respect to the carboxy 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 resin solution. After cooling to room temperature, about 2 g of the photosensitive resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by mass in the previously synthesized photosensitive resin solution. A photosensitive resin (B1-3) solution was prepared by adding propylene glycol monomethyl ether acetate. The binder resin (B1-3) had a non-volatile acid value of 146 mgKOH / g and a mass average molecular weight (Mw) of 13,000.

<Manufacturing method of coloring composition (single color)>
[Manufacturing Example 1]
(Preparation of coloring composition (R-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Aiga-Mill (“Mini Model M-250 MKII” manufactured by Aiga-Japan) using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (R-1) having a non-volatile component of 24.3% by mass.
Pigment (A1-1): 20.5 parts Resin-type dispersant solution (nonvolatile content 30%): 2.0 parts Binder resin solution (B-1: non-volatile content 20%): 16.0 parts Solvent (NM) ): 61.5 copies

The solvent (NM) was prepared by mixing the following "N1" to "N6" in parts by mass.
"N1" PGMAc 30 parts "N2" Cyclohexanone 30 parts "N3" Ethyl 3-ethoxypropionate 10 parts "N4" Propylene glycol monomethyl ether 10 parts "N5" Cyclohexanol acetate 10 parts "N6" Diproprene glycol methyl ether 10 copies of acetate

[Manufacturing Examples 2 to 14]
(Preparation of coloring compositions (R-2) to (R-14))
Coloring compositions (R-2) to (R-14) were prepared in the same manner as in Production Example 1 except that the material types and masses were changed as shown in Table 1.

<Manufacturing method of coloring composition (mixing of coloring materials)>
[Manufacturing Example 101]
(Preparation of coloring composition (X-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 colored composition (X-1).
Coloring composition solution (R-1: non-volatile content 24.3%): 63 parts Coloring composition solution (R-7: non-volatile content 24.3%): 35 parts binder resin solution (B-1: non-volatile content 20%) ): 1 part Solvent (NM): 1 part

[Manufacturing Examples 102 to 113]
(Preparation of coloring composition (X-2 to 13))
Coloring compositions (X-2 to 13) were produced in the same manner as in Production Example 101, except that the material types and masses were changed as shown in Table 2.

<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 solution (X-1: non-volatile content 24.0%): 50.0 parts binder resin solution (B1-1: non-volatile content 20%): 7.0 parts thermosetting resin solution (E-1: epoxy) 40%): 0.8 part photopolymerizable compound (CM): 1.0 part photopolymerizable compound (C-1-1): 2.2 part photopolymerizable initiator (DM): 1. .89 parts Sensitizer (GM): 0.2 parts Thiol-based chain transfer agent (HM): 0.4 parts Polymerization inhibitor (IM): 0.01 parts Ultraviolet absorber (F-M) 1): 0.1 part Antioxidant (J-M): 0.1 part Leveling agent (KM: Non-volatile content 3%): 1.0 part Storage stabilizer (LM): 0.1 part Adhesion improver ((MM): 0.2 parts Solvent (NM): 35.0 parts

[Examples 2-29, Comparative Examples 1-2]
(Preparation of Photosensitive Coloring Compositions (Y-2) to (Y-31))
The photosensitive coloring composition (Y-2) was carried out 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 Tables 3-1 and 3-2. ~ (Y-31) were prepared respectively.

<Polymerizable compound (C)>
(CM) Hereinafter, "C1" to "C7" were mixed in equal amounts to obtain a photopolymerizable compound (CM).
"C1" trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
"C2" dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
"C3" polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
"C4" Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

"C5" Pentaerythritol triacrylate (432 parts, hexamethylene diisocyanate 84 parts) 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 form a (meth) acryloyl group. A product containing the polyfunctional urethane acrylate "C5" having the above was obtained. The proportion of the polyfunctional urethane acrylate "C5" in the product was 70% by mass, and the balance was made of another photopolymerizable monomer. It occupies. In addition, a coat in which the isocyanate group is not present in the reaction product was confirmed by IR analysis.

"C6" ethoxylated bisphenol A diacrylate
[NK Ester ABE-300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
"C7" ethoxylated isocyanuric acid triacrylate
[NK Ester A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)]
<Alicyclic compound (C-1) having two polymerizable unsaturated groups>
(C-1-1) Tricyclodecanedimethanol diacrylate [NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)]
(C-1-2) Tricyclodecanedimethanol dimethacrylate [NK ester DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.)]

<Photopolymerizable initiator (D)>
(DM) Hereinafter, "D1" to "D8" were mixed in equal amounts to obtain a photopolymerization initiator (DM).
"D1" 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
"D2" 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(D3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
"D4"2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurokin Kasei Co., Ltd.)]
"D5" p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
"D6" ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan Ltd.)]
"D7" 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
"D8" bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]

<Thermosetting compound (E-1) solution>
1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2'-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Co., Ltd .: EHPE3150, epoxy equivalent 170-190 g / eq) is dissolved in PIGMAc. The non-volatile content was adjusted to 40% to prepare a thermosetting compound (E-1) solution.

<UV absorber (F)>
(F-1): 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol
[TINUVIN326 (manufactured by BASF Japan Ltd.)]
(F-2) 2- (2H-benzotriazole2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan Ltd.)]

<Sensitizer (G)>
(GM) Hereinafter, "G1" and "G2" were mixed in the same amount to prepare a sensitizer (GM).
"G1" 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
"G2"4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]

<Thiol chain transfer agent (H)>
(HM) Hereinafter, "H1" to "H5" were mixed in equal amounts to obtain a thiol-based chain transfer agent (HM).
"H1" Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
"H2" trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
"H3" pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
"H4" trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
"H5" Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]

<Polymerization inhibitor (I)>
(IM) Hereinafter, "I1" to "I3" were mixed in equal amounts to obtain a polymerization inhibitor (IM).
"I1" 3-Methylcatechol "I2" Methylhydroquinone "I3" t-Butylhydroquinone

<Antioxidant (J)>
(J-M) Hereinafter, "J1" to "J5" were mixed in equal amounts to prepare an antioxidant (J-M).
"J1" pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate "J2"3,3'-dioctadecyl thiodipropanoate "J3" tris [2,4-di-( t) -Butylphenyl] phosphine "J4" bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate "J5" p-octylphenyl salicylate

<Leveling agent (KM)>
Big Chemi-manufactured "BYK-330" 1 copy,
A mixed solution in which 1 part of "Mega Fvck F-551" manufactured by DIC and 1 part of "Emargen 103" manufactured by Kao Corporation are dissolved in 97 parts of PGMAc.

<Storage stabilizer (L)>
(LM) Hereinafter, "L1" and "L2" were mixed in equal amounts to prepare a storage stabilizer (LM).
"L1" 2,6-bis (1,1-dimethylethyl) -4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
"L2" triphenylphosphine ("TPP" manufactured by Hokuko Chemical Industry Co., Ltd.)

<Adhesion improver (M)>
(MM) Hereinafter, "M1" to "M4" were mixed in the same amount to prepare a silane coupling agent (MM).
"M1" 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
"M2" 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
"M3" N-2- (aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
"M4" 3-mercaptopropyltrimethoxysilane
[Shin-Etsu Silicon Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]

<Evaluation of photosensitive resin composition>
The photosensitive resin compositions (Y-2 to 31) were evaluated as follows. The 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

<Evaluation of fine line adhesion>
The photosensitive resin composition is rotated on a glass substrate (Glass Eagle 2000 manufactured by Corning Inc.) having a thickness of 100 mm × 100 mm and 0.7 mm using a spin coater so that the dry film thickness is 2.4 μm. It was coated and prebaked at 90 ° C. for 120 seconds. Next, the substrate was cooled to room temperature, spray-developed with a 0.04% potassium hydroxide aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. The obtained substrate was observed with an optical microscope to confirm the minimum line width of the remaining stripe pattern.
⊚: Fine lines of 10 μm or less remain ○: Fine lines of 10 μm or less do not remain, but thin lines of 30 μm or less remain Δ: Fine lines of 30 μm or less do not remain, but thin lines of 50 μm or less remain X: No thin lines of 50 μm or less remain

<Evaluation of development speed>
The photosensitive resin composition is rotated on a glass substrate (Glass Eagle 2000 manufactured by Corning Inc.) having a thickness of 100 mm × 100 mm and 0.7 mm using a spin coater so that the dry film thickness is 2.4 μm. It was coated and prebaked at 90 ° C. for 120 seconds. Next, after cooling this substrate to room temperature, spray development was performed using a 0.04% sodium carbonate aqueous solution at 23 ° C., the time until the coating thickness was dissolved and disappeared was measured, and the development speed of the photosensitive resin composition was determined. evaluated. The evaluation ranks are as follows.
⊚: less than 20 seconds ○: 20 seconds or more, less than 30 seconds Δ: 30 seconds or more, less than 40 seconds ×: 40 seconds or more

[Filter segment formation]
The obtained photosensitive coloring composition is applied to a glass substrate having a length of 10 cm and a width of 10 cm by a spin coating method, and then heated in a clean oven at 70 ° C. for 15 minutes to remove the solvent to obtain a film of about 2 μm. It was. Next, after cooling the glass substrate to room temperature, ultraviolet rays were exposed through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 30 minutes to prepare a filter segment. The spray development was performed on the coating film of each photosensitive coloring composition in the shortest time during which a pattern could be formed so that no development residue remained, and this was set as the appropriate development time. The film thickness of the coating film was determined by using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

<Pattern shape evaluation>
[Linearity evaluation]
The linearity of the pattern at the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an optical microscope. The evaluation criteria are as follows.
◯: Good linearity △: Partially poor linearity (slightly chipped)
×: Poor linearity

[Cross-sectional shape evaluation]
The cross section of the pattern at the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an electron microscope. The evaluation criteria are as follows. The turn cross section has a good forward taper.
〇: Forward taper shape with gentle cross section Δ: Forward taper shape with cross section ×: Reverse taper shape with reverse cross section

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 (7)

A photosensitive coloring composition containing a colorant (A), a binder resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
40 to 70% by mass of the colorant (A) is contained in 100% by mass of the non-volatile content of the photosensitive coloring composition.
The binder resin (B) contains a photosensitive resin (B1) having an acid value of 100 to 300 mgKOH / g and a weight average molecular weight of 2,000 to 20,000.
A photosensitive coloring composition in which the polymerizable compound (C) contains an alicyclic compound (C-1) having two polymerizable unsaturated groups. The photosensitive coloring composition according to claim 1, wherein the colorant (A) contains an aluminum phthalocyanine pigment (A1). The photosensitive coloring according to claim 1 or 2, wherein the photosensitive resin (B1) contains an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in the side chain selected from the following (I) and (II). Composition.
(I) An alkali-soluble resin obtained by reacting a product of an epoxy group in an epoxy group-containing resin with a carboxy group-containing monomer with a polybasic acid anhydride.
(II) An alkali-soluble resin which is a reaction product of a carboxy group in a carboxy group-containing resin and an epoxy group-containing monomer. The photosensitive coloring composition according to any one of claims 1 to 3, further comprising a thermosetting resin (E). The photosensitive coloring composition according to any one of claims 1 to 4, further comprising an ultraviolet absorber (F). A color filter comprising a base material and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 5. A liquid crystal display device including the color filter according to claim 6.

Images