JP2021196561A - Photosensitive coloring composition, color filter, and image display device - Google Patents

Abstract

To provide a photosensitive coloring composition which has good storage stability as a coloring composition and a photosensitive coloring composition, and enables dissolution of a display failure of a liquid crystal display device caused by zinc phthalocyanine, and a color filter and a liquid crystal display device formed using the photosensitive coloring composition.SOLUTION: A coloring composition is provided, including a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersion agent, a polymerizable compound, a photopolymerization initiator, and a binder resin.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive coloring composition that can be used for forming a color filter used in a liquid crystal display device, an organic EL display device, a solid-state image pickup device, or the like.

Examples of the operation method of the liquid crystal display device include a twisted nematic (TN) method, a horizontal electric field method (In Plane Switching: IPS method), and a vertical alignment method (VA method). Among these, the IPS system has a feature of having a wide viewing angle. In the IPS method, unlike other methods, a common electrode is not formed on the second transparent substrate on which the color filter is formed. Therefore, the IPS type liquid crystal display device is directly affected by the electrical characteristics of the color filter pixels, and has a problem of causing display defects.

Therefore, Patent Documents 1 and 2 disclose a photosensitive coloring composition containing a zinc phthalocyanine pigment, a copper phthalocyanine pigment, and a specific dispersant.

Japanese Unexamined Patent Publication No. 2018-10210 Japanese Unexamined Patent Publication No. 2018-45189

However, the zinc phthalocyanine pigment used in the conventional photosensitive coloring composition has good green color-developing property, but has photoconductivity because it is an ionic substance. Therefore, when using a liquid crystal display device, when the transverse electric field that drives the liquid crystal molecules penetrates the color filter, the light charge generated in zinc phthalocyanine accumulates in the colored layer and disturbs the transverse electric field, thus solving the problem of display failure. It wasn't done.

An object of the present invention is to provide a photosensitive coloring composition capable of producing a color filter in which display defects are unlikely to occur while using a zinc phthalocyanine pigment.

The photosensitive coloring composition of the present invention contains a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin.

According to the above invention, it is possible to provide a photosensitive coloring composition, a color filter, and an image display device capable of producing a color filter in which display defects are unlikely to occur while using zinc phthalocyanine.

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

The terminology of the present specification is defined. When the terms "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are used, unless otherwise specified, they 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, for example, a vinyl group, a (meth) acryloyl group, or the like. The monomer is a polymerizable unsaturated group-containing compound.

The photosensitive coloring composition of the present invention contains a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin. The photosensitive coloring composition is preferably used by coating it on a substrate to form a film. It is preferable that the coating film is patterned by a photolithography method and used as a green filter segment constituting a color filter.

In the photosensitive coloring composition of the present invention, when an aluminum phthalocyanine pigment (B) and a copper phthalocyanine pigment (C) are used in combination with a zinc phthalocyanine pigment (A) which is an ionic substance and adversely affects electrical characteristics, the composition is dielectric. In addition to improving the characteristics and improving the redness of the entire display screen, by using the copper phthalocyanine pigment (C), in the color range where high coloring power such as digital cinema (DCI) standard and Adobe standard is required. Color reproduction is possible, and it is possible to develop colors in a wider color range. As a result, the film formed from the photosensitive coloring composition can achieve both green color development and display characteristics.

<Zinc phthalocyanine pigment (A)>
The zinc phthalocyanine pigment (A) is a phthalocyanine pigment in which the central metal Q in the compound represented by the following general formula (1) is zinc (Zn).

General formula (1)

(In the general formula (1), Q represents Zn of the central metal, and X _{1 to} X ₁₆ independently represent atoms of H, Cl, Br, and I.)

The zinc phthalocyanine pigment (A) is preferably a halogenated compound represented by the following general formula (1). This improves the brightness and coloring power.

<Aluminum phthalocyanine pigment (B)>
The aluminum phthalocyanine pigment (B) is a phthalocyanine pigment having an aluminum (Al) atom in the central metal. As the aluminum phthalocyanine pigment (B), for example, the pigment described in JP-A-2017-1111398 is preferable. When used, display characteristics and brightness are improved.

The aluminum phthalocyanine pigment (B) preferably halogenates the pigment described in JP-A-2017-11138. As a result, in addition to further improving the brightness, the coloring power is also improved.

<Copper phthalocyanine pigment (C)>
The copper phthalocyanine pigment (C) is a phthalocyanine pigment in which the central metal Q in the compound represented by the following general formula (2) is copper (Cu). When this is used, the coloring power is improved.

General formula (2)

(In the general formula (2), Q represents Cu as the central metal, and X _{1 to} X ₁₆ independently represent the atoms of H, Cl, Br, and I.)

The copper phthalocyanine pigment (C) preferably halogenates the compound represented by the general formula (2). This improves the brightness.

The zinc phthalocyanine pigment (A), the copper phthalocyanine pigment (C) and the aluminum phthalocyanine pigment (B) can be used alone or in combination of two or more.

<Yellow pigment (D)>
The photosensitive coloring composition can contain the yellow pigment (D). By containing the yellow pigment, not only the display characteristics can be improved, but also the coloring power and the brightness can be improved.

The yellow pigment is, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233 and the like. Among these, C.I. I. Pigment Yellow 138, 139, 150, 185, 231 and 233 are preferred.

<Other pigments>
In the present specification, other pigments can be used as the colorant in addition to the above pigments. Examples of other pigments include the following organic pigments and inorganic pigments. The following organic pigments can be used as colorants used for blue filter segments, red filter segments, etc., in addition to color adjustment of green filter segments. Hereinafter, specific examples of organic pigments are shown by color index numbers.

The red pigment is, 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, Examples thereof include pigments described in 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. 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, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844. More preferably, C.I. I. Pigment Red 177, 254, 291, 295, 296, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844.

The red pigment is C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments, red pigments, green pigments, blue pigments and yellow pigments can be used in combination. Yellow pigment can be used together.

The blue pigment is, for example, C.I. I. Pigment blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and the like. Red pigments, orange pigments, green pigments, purple pigments, and yellow pigments can be used in combination.

Purple pigments and red pigments are, for example, C.I. I. Pigment Violet 1, 19, 23 and the like. As the purple pigment, a red pigment, an orange pigment, a green pigment, a blue pigment, and a yellow pigment can be used in combination.

<Pigment miniaturization>
In the present invention, it is preferable that the organic pigment is subjected to a miniaturization treatment and then mixed with other raw materials. Examples of the miniaturization treatment method include wet grinding, dry grinding, dissolution and precipitation method and the like. Among these, salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size of the organic pigment after the miniaturization 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 diameter is an average value of about 20 particles arbitrarily selected from a magnified image of a TEM (transmission electron microscope). If there is a vertical axis length and a horizontal axis length of the particle, the vertical axis length is used.

The salt milling treatment involves batch-type or continuous mixing of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, for example, a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, or the like. This is a 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, sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120 ° C. or higher because it is difficult to volatilize due to a temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and triethylene glycol. Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

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

Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc flower, 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.

<Dye>
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium-dye dyes, building dyes, sulfide dyes and the like. Further, a derivative of a dye and a lake pigment obtained by converting a dye into a lake can also be mentioned.

The dye is preferably used as a salt-forming compound. The salt-forming compound is a salt-forming compound of an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a resin component having an amino group and a salt-forming compound such as an acidic dye; Salt-forming compounds of acidic dyes and compounds having onium bases; salt-forming compounds of basic dyes with organic acids, perchloric acids, or metal salts thereof. Among these, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments. The compound having an onium base is preferably a resin having a cationic group in the side chain.

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

<Dye derivative>
As used herein, dye derivatives can be used as needed. When the dye derivative is adsorbed on the surface of the organic pigment, the surface of the organic pigment has polarity and becomes easily compatible with the dispersant, so that the dispersibility of the organic pigment is further improved. The dye derivative is a compound having an acidic group, a basic group, a neutral group and the like in the organic dye residue. The dye derivative has, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and a basic substituent such as an amine salt thereof, a sulfonamide group, or a tertiary amino group at the terminal. 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.

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

The content of the dye derivative 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 organic pigment.

By adding a dye derivative to the pigment and performing miniaturization treatment such as acid pacing, acid slurry, dry milling, salt milling, and solvent salt milling, the dye derivative is adsorbed on the pigment surface and the dye derivative is not added. The primary particles of the pigment can be made finer than in the case.

Examples of the miniaturization treatment include wet dispersion using two rolls, three rolls, beads and the like.

<Dispersant>
Examples of the dispersant include a low molecular weight dispersant and a resin type dispersant, and a resin type dispersant is preferable. The resin-type dispersant has a colorant-affinitive moiety that adsorbs to the organic pigment and a relaxation moiety that has high affinity with components other than the colorant and causes steric repulsion between the dispersed particles.
The resin type dispersant may be, for example, a urethane dispersant such as polyurethane, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, or a polycarboxylic material. With ammonium acid salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their variants, poly (lower alkyleneimine) and polyesters with free carboxyl groups. Oily dispersants such as amides and salts thereof formed by the reaction of, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer , Polyvinyl alcohol, water-soluble resin such as polyvinylpyrrolidone, water-soluble polymer compound, polyester type, modified polyacrylate type, ethylene oxide / propylene oxide addition compound, phosphoric acid ester type and the like.

In addition, examples of the functional group type dispersant include an acidic functional group-containing resin type dispersant and a basic functional group-containing resin type dispersant.
The acidic functional group-containing resin-type dispersant is preferably, for example, a resin-type dispersant having an aromatic carboxylic acid structure. It is described in JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651 and the like.

The basic functional group-containing resin-type dispersant contains, for example, a nitrogen atom-containing graft copolymer or a nitrogen atom-containing functional group having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples thereof include acrylic block copolymers and urethane polymer dispersants. An acidic functional group-containing resin-type dispersant and a basic functional group-containing resin-type dispersant can also be used in combination.

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

The content of the dispersant is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the organic pigment.

<Binder resin>
The binder resin is preferably a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin is preferably a thermoplastic resin or a photosensitive resin. Further, the binder resin preferably has alkali solubility. Thereby, the film formed from the photosensitive coloring composition can be patterned by the photolithography method. Further, the photosensitive resin having no alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

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

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

Examples of the alkali-soluble resin include resins having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble thermoplastic resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, or an ethylene / (meth) acrylic acid copolymer. , Or isobutylene / (anhydrous) maleic acid copolymer and the like. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of improving developability, heat resistance, and transparency.

<Thermoplastic resin>
The thermoplastic resin is a resin that does not have alkali solubility. The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

<Alkali-soluble photosensitive resin>
The alkali-soluble photosensitive resin has photosensitive because it has a polymerizable unsaturated group. The alkali-soluble photosensitive resin may be alkali-soluble and may have photosensitivity, and a known resin can be used. Therefore, the resin synthesized by the following method (i) or (ii) is preferable. When an alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation to increase the crosslink density, so that the chemical resistance of the coating film is improved.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin can be mentioned. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

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.

The monocarboxyl 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. Examples include monocarboxylic acids such as the body.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

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 acrylates, benzyl (meth) acrylates, phenoxyethyl (meth) acrylates, phenoxydiethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, or ethoxypolyethylene glycol (meth) acrylates,
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. Classes styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate, etc. Can be mentioned.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide Hexanoate, N-substituted maleimides such as N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethyleneoxide (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.

In the method (ii), for example, a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers are polymerized to prepare a polymer. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin can be mentioned.

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 superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, 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. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable, and 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.

Examples of the other monomer include a phosphoric acid ester group-containing monomer and the like in addition to the other monomer exemplified in the above method (i).

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

The above-mentioned raw materials for the binder resin can be used alone or in combination of two or more. Further, the binder resin can be used alone or in combination of two or more.

The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant. 20 parts by mass or more is preferable because the film forming property and various resistances are good, and 400 parts by mass or less is preferable because the colorant concentration is high and good color characteristics can be exhibited.

The weight average molecular weight (Mw) of the binder resin is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The value of Mw / Mn is preferably 10 or less. Mn is a number average molecular weight.

The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. With an appropriate acid value, alkali solubility, adhesion, and residue suppression can be highly balanced.

<Polymerizable compound>
Examples of the polymerizable compound include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

The acid group-containing monomer 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 polyhydric carboxylic acid and a monohydroxyalkyl (meth). ) Examples thereof include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarboxylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by reaction.

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

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

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth). ) Acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, Trimethylol propanthry (meth) acrylate, Phenoxy Tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocianul Acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A Diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylol Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, and urethane acrylate of melamine and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta. Examples thereof include erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

The polymerizable compound 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% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

<Photopolymerization initiator>
The photopolymerization initiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 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-butanone, etc. Acetphenone compounds; 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, acrylicized benzophenone , 4-Benzoyl-4'-methyldiphenylsulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone. , Isoxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl)- s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6- Triazine compounds such as triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyl oxime)], or oxime esters such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) Compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphinoxide or diphenyl-2,4,6-trimethylbenzoylphosphinoxide; 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone. Kinone-based compounds such as; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds and the like can be mentioned. Among these, oxime ester compounds are preferable.

(Oxime ester compound)
The oxime ester compound breaks the NO bond of the oxime by absorbing ultraviolet rays, and produces an iminyl radical and an arcroxy 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 concentration of the colorant in the photosensitive coloring composition is high, the ultraviolet transmittance of the film may be low and the degree of curing of the film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency.

The oxime ester compound is described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-0372223, JP-A-2010-215575, JP-A-2011-02998, and the like. Examples thereof include ester-based photopolymerization initiators.

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

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

<Sensitizer>
Examples of the sensitizer include unsaturated ketones such as chalcone derivatives and 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, thiadine derivatives, oxadin derivatives, indolin derivatives. , Azulene derivative, Azurenium derivative, Squalylium derivative, Porphyrin derivative, Tetraphenylporphyrin derivative, Triarylmethane derivative, Tetrabenzoporphyrin derivative, Tetrapyrazinoporphyrazine derivative, Phthalocyanin 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 Mihiler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylgrioxylates, benzyls, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like can be mentioned. Among these, a thioxanthone derivative, a Michler ketone derivative, and a carbazole derivative are preferable. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis ( Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N -Ethylcarbazole and the like are more 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 with respect to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

<Thiol chain transfer agent>
The photosensitive coloring composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the photosensitive coloring composition is improved.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photo-cure from the surface of the film to the deepest part.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propantristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Tristrimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And the like, preferably ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

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 0.1 to 10% by mass, more preferably 0.1 to 3% 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 and the tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating film.

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

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl. Resorcinol, 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 Alkyl catechol compounds such as -butyl catechol, 3,5-di-tert-butyl catechol, 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, phosphin compounds such as tributylphosphin, trioctylphosphin, tricyclohexylphosphin, triphenylphosphin, tribenzylphosphin, trioctylphosphinoxide, triphenylphosphinoxide and the like. Examples thereof include phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, fluoroglucolcin and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 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 film, pattern resolution, etc. are improved.

<UV absorber>
The photosensitive coloring composition may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorber may be an oligomer or a polymer.

Benzotriazole 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 parts 2-methoxy-1-methylethyl acetate and 95 parts benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1) -Mixed of 4-hydroxy, C7-9 side chain and linear alkyl ester, 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) Pharmon, 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.

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- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-. Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Examples thereof include syroxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

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

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating film is further improved, and good resolution can be obtained.

<Thermosetting compound (E)>
The photosensitive coloring composition can contain a thermosetting compound (E). During the post-baking step when producing a color filter using the photosensitive coloring composition, the thermosetting compound (E) is thermoset to increase the crosslink density of the coating film, and the heat resistance is improved. This suppresses pigment aggregation in the post-baking process and improves the contrast ratio.

The thermosetting compound (E) may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of the thermosetting compound (E) include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferable.

The content of the thermosetting compound (E) is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. When an appropriate amount is contained, the crosslink density of the coating film is increased and the heat resistance is further improved.

(Hardener)
The photosensitive coloring composition may contain a curing agent (curing accelerator). The curing agent assists in curing the thermosetting compound (E).
Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like.
The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2). -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- Examples thereof include S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.).

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

The amount of the curing agent used is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (E).

<Antioxidant>
The photosensitive coloring composition may contain an antioxidant. As the antioxidant, the film formed from the photosensitive coloring composition can prevent yellowing due to oxidation by the thermal process at the time of thermosetting or ITO annealing, and can suppress the decrease in the transmittance of the film. In particular, when the concentration of the colorant in the photosensitive coloring composition is high, the content of the polymerizable compound is relatively reduced. Therefore, if the amount of the photopolymerization initiator is increased or the thermosetting compound is blended, the film turns yellow. easy. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and suppress a decrease in the transmittance of the coating film.

The antioxidant is a compound having a radical catching function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol-based compounds, hindered amine-based compounds, phosphorus-based compounds, sulfur-based compounds, hydroxylamine-based compounds, and the like. The antioxidant is preferably a compound that does not contain a halogen atom. Among these, hindered phenol-based compounds, hindered amine-based compounds, phosphorus-based compounds, and sulfur-based compounds are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

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.

<Leveling agent>
The photosensitive coloring composition may contain a leveling agent. As a result, the wettability to the transparent substrate at the time of forming the film and the drying property of the film are further improved. Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and the like.

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

The content of the surfactant is preferably 0.001 to 2.0 parts by mass, more preferably 0.005 to 1.0 part by mass in the non-volatile content of the photosensitive coloring composition. Within this range, the balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

<Storage stabilizer>
The photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic acids such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples include phosphine and phosphite.

The content of the storage stabilizer is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the colorant.

<Adhesion improver>
The photosensitive coloring composition may contain an adhesion improver. This further improves the adhesion between the coating film and the base material. In addition, the photolithography method facilitates the formation of narrow patterns. Examples of the adhesion improver include a silane coupling agent and the like.

Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-) Aminosilanes such as dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Mercapts such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include isocyanates such as sulfides and 3-isocyanuspropyltriethoxysilane.

The content of the adhesion improver 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 organic pigment.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition is subjected to a dispersion treatment using, for example, an organic pigment, a dispersant, a solvent, or the like to prepare a pigment dispersion. When a dispersion aid such as a dye derivative is used in combination during the dispersion treatment, the organic pigment can be dispersed more finely, and when the organic pigment has high solubility in a solvent, the dispersion treatment may not be required. When two or more kinds of pigments are used in combination, a pigment dispersion can be prepared for each pigment type and then mixed. In addition, a pigment dispersion can be collectively produced by using a plurality of pigments.
Next, a polymerizable compound, a photopolymerization initiator, and a binder resin are blended with the pigment dispersion and mixed to obtain a photosensitive coloring composition. 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.

<Solvent>
The photosensitive coloring composition may contain a solvent. As a result, the viscosity of the photosensitive coloring composition can be easily adjusted, so that a film having a smooth surface can be easily formed. The solvent may be appropriately selected according to the purpose of use and may contain an appropriate amount.

The solvent is, for example, 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 and -O -, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Among these, a 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 more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are further preferable.

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

<Removal of coarse particles>
The photosensitive coloring composition is prepared by means such as centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration by a sintering filter or a membrane filter, and coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm. It is preferable to remove the above coarse particles and mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
As used herein, a color filter comprises a substrate (also referred to as a substrate) and a filter segment formed of a photosensitive coloring composition. The color filter 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 further have a magenta color filter segment, a cyan color filter segment, and a yellow filter segment as the color filter segment. Examples of the substrate include a transparent substrate and a reflective 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 substrate and then forms a filter segment. A thin film transistor (TFT) can be formed on the substrate 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 formation of the filter segment can be produced by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. The most preferred photolithography method is described herein.

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 to develop the developer, 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.

Examples of the coating device include a spray coat, a spin coat, a slit coat, a roll coat 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. Further, a defoaming agent or a surfactant can be added to the developing solution.

The color filter is bonded to the facing substrate using a sealing agent, the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. By laminating, a liquid crystal display device is manufactured. This liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convensend bend (OCB). It is preferable to use it in a liquid crystal display mode in which colorization is performed using a color filter such as.

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

<Image display device>
The image display device of the present specification includes a color filter. The image display device preferably further includes a light source. A liquid crystal display device will be described as an example of the image display device.
The liquid crystal display device includes a color filter 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 constituting the color filter 22 are separated by a black matrix (not shown).

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

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

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in a resin package of a blue LED, and the wavelength at which the emission intensity becomes maximum in the range of 430 nm to 485 nm ( It has λ3), has a wavelength (λ4) that maximizes emission intensity in the range of 530 nm to 580 nm, has a wavelength (λ5) that maximizes emission intensity in the range of 600 nm to 650 nm, and has a wavelength. The ratio (I4 / I3) of the emission intensity I3 at the wavelength λ3 and the emission intensity I4 at the wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at the wavelength λ3 and the emission intensity I5 at the 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 within the range of 430 nm to 485 nm, and is in the range of 530 nm to 580 nm. Spectral characteristics having a peak wavelength (λ2) of the second emission intensity within, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ1 and 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 of 2 is preferable.

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

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

The image display device of the present specification 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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, "part" is "mass part", and "%" is "mass%". In principle, the blending amount in the table is by mass.

Each measurement method will be described below.

(Average primary particle size of pigment)
A solvent (methoxypropyl acetate) is added to the pigment powder, a small amount of a dispersant (Disperbyk-161: manufactured by Big Chemie) is added, and the sample is prepared by ultrasonic treatment for 1 minute. Next, using a transmission electron microscope (TEM), three photographs (for three fields of view) in which the primary particles of 100 or more pigments can be confirmed are created, and the sizes of the 100 primary particles are measured in order from the upper left. .. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is taken as the primary particle diameter of the pigment particles, and a total of 20 distributions are created in increments of 5 nm. The median value in increments of 5 nm (for example, 8 nm in the case of 6 nm or more and 10 nm or less) is approximated as the particle diameter of those particles, and the number average particle diameter is calculated by calculating based on each particle diameter and its number.

(Acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve evenly, and use a 0.1 mol / L KOH aqueous solution as a titrator as an automatic titrator (“COM-555” Hiranuma Sangyo Co., Ltd.” The acid value (mgKOH / g) of the resin solution was measured by titration using (manufactured by). 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 content concentration of the resin solution.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin is converted to polystyrene measured by using a TSKgel column (manufactured by Tosoh) and a GPC (manufactured by Tosoh, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

(Double bond equivalent of resin)
The double bond equivalent was calculated as the mass of the resin per 1 mol of double bond.

<Manufacturing method of colorant>
[Zinc phthalocyanine colorant (A-1)]
C.I. of zinc phthalocyanine pigment (A). I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture is put into 2000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating to about 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 a day. Then, 96 parts of a zinc phthalocyanine-based colorant (A-1) was obtained.

[Aluminum phthalocyanine colorant (B-1)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was changed to an aluminum phthalocyanine pigment (B) 1 having the following structure manufactured according to an example of JP-A-2017-1111398. The same procedure as in the production of A-1) was carried out to obtain 96 parts of an aluminum phthalocyanine-based colorant (B-1).

(Aluminum phthalocyanine pigment (B) 1)
(Aluminum phthalocyanine pigment (B) 1 of the following formula (1) was produced according to an example of JP-A-2017-1111398. The structure is shown below.
Equation (1)

[Aluminum phthalocyanine colorant (B-2)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was changed to an aluminum phthalocyanine pigment (B) 2 having the following structure manufactured according to an example of JP-A-2017-1111398. The same procedure as in the production of A-1) was carried out to obtain 96 parts of an aluminum phthalocyanine-based colorant (B-2).

(Aluminum phthalocyanine pigment (B) 2)
(Aluminum phthalocyanine pigment (B) 2 of the following formula (2) was produced according to an example of JP-A-2017-1111398. The structure is shown below.
Equation (2)

[Aluminum phthalocyanine colorant (B-3)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was changed to an aluminum phthalocyanine pigment (B) 3 having the following structure manufactured according to an example of JP-A-2017-1111398. The same procedure as in the production of A-1) was carried out to obtain 96 parts of an aluminum phthalocyanine-based colorant (B-3).

(Aluminum phthalocyanine pigment (B) 3)
The aluminum phthalocyanine pigment (B) 3 of the following formula (3) was produced according to an example of JP-A-2017-1111398. The structure is shown below.
Equation (3)

[Aluminum phthalocyanine colorant (B-4)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was changed to an aluminum phthalocyanine pigment (B) 4 having the following structure manufactured according to an example of JP-A-2017-1111398. The same procedure as in the production of A-1) was carried out to obtain 96 parts of an aluminum phthalocyanine-based colorant (B-4).

(Aluminum phthalocyanine pigment (B) 4)
The aluminum phthalocyanine pigment (B) 4 of the following formula (4) was produced according to an example of JP-A-2017-1111398. The structure is shown below.
Equation (4)

[Aluminum phthalocyanine colorant (B-5)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was changed to an aluminum phthalocyanine pigment (B) 5 having the following structure manufactured according to an example of JP-A-2017-1111398, except that the zinc phthalocyanine colorant (zinc phthalocyanine colorant) ( The same procedure as in the production of A-1) was carried out to obtain 96 parts of an aluminum phthalocyanine-based colorant (B-5).

(Aluminum phthalocyanine pigment (B) 5)
(Aluminum phthalocyanine pigment (B) 5 of the following formula (5) was produced according to an example of JP-A-2017-1111398. The structure is shown below.
Equation (5)

[Copper phthalocyanine colorant (C-1)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was used as a copper phthalocyanine pigment (C) in C.I. I. Pigment Green 36 (“LIONOL GREEN 6YK” manufactured by Toyo Color Co., Ltd.) was changed in the same manner as in the production of zinc phthalocyanine colorant (A-1), and 96 parts of copper phthalocyanine colorant (C-1) was produced. Got
[Copper phthalocyanine colorant (C-2)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation) was used as a copper phthalocyanine pigment (C) in C.I. I. Pigment Blue 15: 3 (“Rionol Blue FG-7351” manufactured by Toyo Color Co., Ltd.) was changed in the same manner as the production of zinc phthalocyanine colorant (A-1), and 96 parts of copper phthalocyanine colorant was used. (C-2) was obtained.

[Yellow colorant (D-1)]
C. I. Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), C.I. I. Pigment Yellow 138 (“Paliotor Yellow K0961HD” manufactured by BASF Japan Ltd.) was used in the same manner as for the production of zinc phthalocyanine colorant (A-1), and 96 parts of yellow colorant (D-1) was applied. Obtained.

<Production example of dispersant>
(Manufacturing of Dispersant Solution 1)
A reaction layer equipped with a gas introduction tube, temperature, condenser, and stirrer contains 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAC). The part was charged and replaced with nitrogen gas. The inside of the reaction layer was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAC. It was confirmed by measuring the non-volatile content that 95% or more of the reaction occurred. Next, 19 parts of pyromellitic acid anhydride, 50 parts of PGMAC, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the reaction was carried out at 100 ° C. for 7 hours. I let you. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Next, PGMAC was added so as to have a non-volatile content of 40 parts and diluted to obtain a dispersant solution 1 having an acid value of 70 mgKOH / g and a weight average molecular weight (Mw) of 8500.

<Production example of binder resin>
(Preparation of binder resin solution 1)
196 parts of cyclohexanone was charged 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 dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) , 2,2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. Next, PGMAC was added so that the non-volatile content was 20 parts to obtain a binder resin solution 1 having a weight average molecular weight (Mw) of 26000.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged 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 dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a resin solution. Next, for the entire amount of the obtained resin solution, nitrogen gas was stopped, and the mixture was stirred while injecting dry air for 1 hour, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenzu MOI manufactured by Showa Denko KK). A mixture of 6.5 parts, 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, cyclohexanone was added so that the non-volatile content was 20 parts to obtain a binder resin solution 2 having a weight average molecular weight (Mw) of 18,000.

(Preparation of binder resin solution 3)
182 g of PGMAC 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, the temperature was raised to 100 ° C., and then 70.5 g of benzyl methacrylate. In a mixture consisting of (0.40 mol), 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 136 g of PGMAC. A solution containing 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol parts with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110 ° C. for 6 hours, and then the reaction was terminated. Next, cyclohexanone was added so that the non-volatile content was 20 parts to obtain a binder resin solution 3 having a weight average molecular weight (Mw) of 13,000.

(Preparation of binder resin solution 4)
Put 100 parts of PGMAC in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirrer in a separable 4-neck flask, heat to 120 ° C while injecting nitrogen gas into the vessel, and use the dropping tube at the same temperature. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate and 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours, and the non-volatile acid value = 0. The reaction was terminated when the temperature reached 8.6, and 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were further added, and the reaction was carried out at 120 ° C. for 4 hours to complete the reaction. Next, PGMAC was added so that the non-volatile content was 20 parts to obtain a binder resin solution 4 having a weight average molecular weight (Mw) of 12,000.

<Manufacturing method of colorant dispersion>
[Zinc phthalocyanine colorant dispersion (P-1)]
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colorant dispersion (P-1) was prepared by filtering with the filter of.
Zinc phthalocyanine colorant (A-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 parts

[Aluminum phthalocyanine-based colorant dispersion (P-2)]
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colorant dispersion (P-2) was prepared by filtering with the filter of.
Aluminum phthalocyanine colorant (B-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 parts

[Aluminum phthalocyanine-based colorant dispersion (P-3 to P-6)]
Hereinafter, the colorant dispersions (P-3 to P-6) were prepared in the same manner as the colorant dispersion (P-2) except that the aluminum phthalocyanine colorant was changed to the aluminum phthalocyanine colorant shown in Table 1.

[Copper phthalocyanine colorant dispersion (P-7)]
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colorant dispersion (P-7) was prepared by filtering with the filter of.
Copper phthalocyanine colorant (C-1): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 parts

[Copper phthalocyanine colorant dispersion (P-8)]
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colorant dispersion (P-8) was prepared by filtering with the filter of.
Copper phthalocyanine colorant (C-2): 12.0 parts Dispersant solution 1: 10.0 parts Binder resin solution 1: 25.0 parts PGMAC: 53.0 parts

[Example 1]
(Photosensitive coloring composition (L-1))
The following mixture was stirred and mixed so as to be uniform, then filtered through a 5.0 μm filter and mixed to prepare a photosensitive coloring composition (L-1).
Zinc phthalocyanine-based colorant dispersion (P-1): 28.93 parts Aluminum phthalocyanine-based colorant dispersion (P-2): 16.88 parts Copper phthalocyanine-based colorant dispersion (P-7): 2.41 Part Binder resin solution 2: 2.24 part Binder resin solution 3: 2.20 part Binder resin solution 4: 2.13 part Polymerizable compound 1 ("KAYARAD DPCA-30" manufactured by Nippon Kayakusha): 2.25 part Photopolymerization Initiator 1 (BASF Japan, Inc. "Irgacure OXE-01")
: 0.15 part Photopolymerization Initiator 2 (“Irgacure OXE-04” manufactured by BASF Japan Ltd.)
: 0.15 part thiol chain transfer agent 1 (pentaerythritol tetrakisthiopropionate)
: 0.05 part Antioxidant 1 (ADEKA's "ADEKA STAB AO-80"): 0.05 part UV absorber 1 (ADEKA's "ADEKA STAB LA-29"): 0.05 part Adhesion improver 1 ( Shinetsu Silicone Co., Ltd. "KBM-403"): 0.50 part Leveling agent 1 (Mixed solution in which 1 part of "BYK-330" manufactured by Big Chemie is dissolved in 100 parts of PGMAC): 1.00 part PGMAC: 41.03 parts

[Examples 2 to 24, Comparative Examples 1 to 4]
(Photosensitive coloring composition (L-2 to L-28))
Hereinafter, as shown in Table 2-1, the photosensitive coloring composition (L-1) except that the type and blending amount (part by weight) of the colorant dispersion (P) and the thermosetting compound (E) were changed. ), A photosensitive coloring composition (L-2 to 28) was obtained.

<Thermosetting compound (E)>
Thermosetting compound 1 (E-1)
A solution of "EHPE3150" manufactured by Daicel Co., Ltd. dissolved in 20% by mass of non-volatile content by PGMAC.

<Evaluation of photosensitive coloring composition>
The obtained colored compositions (L-1 to L-28) were tested for storage stability, contrast ratio, and dielectric loss tangent by the following methods. The test results are shown in Table 3.
The meaning of the evaluation rank is as follows.
◎: Extremely good 〇: Good △: Practical use ×: Not suitable for practical use

(Dissipation factor)
The photosensitive coloring composition is coated on a glass substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm, which is vapor-deposited with aluminum for electrodes, using a spin coater so that the film thickness after drying is 2.0 μm. Then, after drying under reduced pressure, a coated substrate was obtained by performing ultraviolet exposure with an integrated light amount of 300 mJ and an illuminance of 30 mW using an ultra-high pressure mercury lamp. Then, the film substrate was heated at 230 ° C. for 1 hour, allowed to cool, ^{and then aluminum for an electrode having an area of 3.464 × 10 -4} m ² was vapor-deposited on the obtained cured film, and the cured film was sandwiched between aluminum electrodes. I made a sample. For the obtained sample, the capacitance from 10 Hz to 1 MHz was measured using an impedance analyzer (“1260 type” manufactured by Solartron) under the condition of overvoltage of 100 mV, and the dielectric loss tangent value at 20 Hz was calculated. , Evaluated according to the following criteria.

(Dissipation factor)
⊚: less than 0.015 〇: 0.015 or more and less than 0.020 ×: 0.020 or more

(Storage stability)
The storage stability of the obtained photosensitive coloring composition was evaluated by the following method.
Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), 25 the initial viscosity of the day after the photosensitive coloring composition was prepared and the viscosity over time accelerated at 40 ° C. for 1 week. The measurements were taken at ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change in viscosity with time was calculated by the following formula, and the storage stability was evaluated in two stages.
[Viscosity change rate over time] = | ([Initial viscosity]-[Viscosity over time]) / [Initial viscosity] | × 100
◯: Viscosity change rate is less than 5% ×: Viscosity change rate is 5% or more

(Contrast ratio)
The coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and heated at 230 ° C. for 20 minutes to obtain a film. At this time, after the heat treatment at 230 ° C., the film thickness was applied by appropriately changing the coating conditions (spin coater rotation speed, time) so that y = 0.645 in the C light source. A color luminance meter (“BM-5A” manufactured by Topcon Co., Ltd.) is used as the luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Co., Ltd.) is used as the polarizing plate. Through the opened black mask, the transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as the contrast ratio.
(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
The judgment criteria are as follows.
⊚: 5500 or more ○: 5000 or more and less than 5500 Δ: 4500 or more and less than 5000 ×: less than 4500

10 Liquid crystal display 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 Plate plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (6)

A photosensitive coloring composition comprising a zinc phthalocyanine pigment (A), an aluminum phthalocyanine pigment (B), a copper phthalocyanine pigment (C), a dispersant, a polymerizable compound, a photopolymerization initiator, and a binder resin. The photosensitive coloring composition according to claim 1, further comprising a yellow pigment (D). In a total of 100% by mass of the zinc phthalocyanine pigment (A), the aluminum phthalocyanine pigment (B), and the copper phthalocyanine pigment (C),
The photosensitive property according to claim 1 or 2, which contains 40 to 80% by mass of the zinc phthalocyanine pigment (A), 19 to 59% by mass of the aluminum phthalocyanine pigment (B), and 1 to 10% by mass of the copper phthalocyanine pigment (C). Coloring composition. The photosensitive coloring composition according to claims 1 to 3, which comprises the thermosetting compound (E). A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 3. An image display device comprising the color filter according to claim 5.

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