KR20200108778A - Pigment dispersion and coloring composition for forming coating layer - Google Patents

Abstract

The present invention relates to a pigment dispersion capable of realizing a color filter having good dispersibility and high contrast, and to a coloring composition for forming a coating film, comprising the same. The pigment dispersion comprises: at least one pigment derivative selected from compounds represented by chemical formula (1); a pigment; a dispersant; and a solvent. In the chemical formula (1), Q represents a dye residue, X represents a methylene group (-CH_2-), an azo group (-N=N-), or a linking group represented by chemical formula (1-2), and in the chemical formula (1) (1-2), * and ** represent a bond hand.

Description

Pigment dispersion and coloring composition for forming a coating film TECHNICAL FIELD [PIGMENT DISPERSION AND COLORING COMPOSITION FOR FORMING COATING LAYER}

The present invention relates to a pigment dispersion and a coloring composition for forming a coating film, and in particular, to a pigment dispersion applicable to a color filter of an image display device and a coloring composition for forming a coating film.

Color filters are widely used as constituent members, such as liquid crystal displays (LCD) and organic electroluminescent (EL) displays, for example. For example, LCDs are widely used in display devices such as monitors, televisions, notebook computers, tablet personal computers, and smart phones. In these display devices, higher image quality is required. For this reason, high contrast has been required for the color filter that constitutes it.

As a color filter, it is widely practiced that a colored photosensitive composition obtained by dissolving or dispersing colorants such as red, green, and blue dyes or pigments in a photosensitive resin is used as a coating liquid, and a coating film is formed by a photolithography process. As described above, as a method for improving the image quality of the color filter, it is considered to increase the color purity by increasing the concentration of the dye or pigment in the colored photosensitive composition. In addition, in order to achieve high contrast, it is considered that large particle diameter particles of the pigment are eliminated, and the pigment is dispersed in the colored photosensitive composition as small particle diameter particles having a wavelength of light or less. However, as the particle diameter decreases, the pigment tends to aggregate and increase in viscosity, and it tends to become difficult to uniformly disperse in the colored photosensitive composition.

Therefore, as a countermeasure, it is widely practiced to improve the dispersibility of particles in the composition by using a pigment derivative or dispersant in which functional groups such as an acidic group are introduced into a pigment such as a pigment (Patent Document 1). In Patent Document 1, a structure based on isoindoline and barbituric acid by using as a dispersant isoindoline derivative having a specific pyrazolone skeleton, which is a sulfonic acid composed of an indoline and a barbitur moiety or a metal salt or quaternary ammonium salt thereof. In a pigment composition using a yellow pigment having a color filter, it becomes possible to make fine particles and high concentration in a dispersion composition without increasing viscosity immediately after dispersion, aggregation, sedimentation, or increase in viscosity over time. (B) It is described that a stable pigment composition can be provided as a colorant for inkjet inks.

However, even if such a dispersant is used, the present situation is that it cannot sufficiently meet the demand for a high-definition display device in the market.

Patent Document 1: Japanese Patent Publication No. 2009-120777

An object of the present invention is to provide a pigment dispersion capable of realizing a color filter having good dispersibility and high contrast, and a coloring composition for forming a coating film comprising the same.

The inventor of the present invention made intensive examination in order to solve the above-described problem. As a result, it was found that the above-described problem was solved by using a pigment derivative having a specific structure.

The first of the present invention relates to a pigment dispersion containing at least one pigment derivative, a pigment, a dispersant, and a solvent selected from compounds represented by the following formula (1).

(In formula (1), Q represents a dye residue, X represents a methylene group (-CH ₂ -), an azo group (-N=N-), or a linking group represented by the following formula (1-2).)

(In formula (1-2), * and ** represent a bonded hand.)

In the embodiment of the present invention, the dye residue Q in formula (1) may be a pigment residue. Further, the dye residue Q may be a residue of a pigment selected from a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment and a quinacridone pigment.

The second of the present invention relates to a coloring composition for forming a coating film comprising the above-described pigment dispersion and a coating film forming component.

In the embodiment of the present invention, a photopolymerizable component may be included as the coating film forming component.

Advantageous Effects of Invention According to the present invention, a pigment dispersion capable of realizing a color filter having good dispersibility and high contrast, and a coloring composition for forming a coating film containing the same can be provided.

Hereinafter, an embodiment of the present invention will be described.

The pigment dispersion according to the embodiment of the present invention contains at least one pigment derivative, a pigment, a dispersant, and a solvent selected from compounds represented by the following formula (1).

(In formula (1), Q represents a dye residue, X represents a methylene group (-CH ₂ -), an azo group (-N=N-), or a linking group represented by the following formula (1-2).)

(In formula (1-2), * and ** represent a bonded hand.)

By using such a specific pigment derivative, it is possible to prevent an increase in viscosity by preventing agglomeration of particles in the pigment dispersion. Moreover, the contrast of the coating film obtained using the coloring composition for coating film formation containing a pigment dispersion can be improved than before. The reason is not clear, but it is assumed that the arrangement of the dispersed particles in the coating film is relatively close to a state where it is difficult to scatter light.

The pigment derivative may be a compound represented by formula (1). In the case where the linking group X is a linking group represented by formula (1-2), the hand bonded to the dye residue Q may be a hand bonded to the side represented by *, or may be a hand bonded to the side represented by **. From the viewpoint of exhibiting the effect more favorably, it is preferable that the connecting hand on the side indicated by * connects with the dye residue Q.

The pigment that serves as the basis for the dye residue Q may be either a pigment or a dye. As the pigment, organic pigments are preferable. For example, anthraquinone pigments, aminoanthraquinone pigments, quinacridone pigments, quinacridone quinone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, Tanthrone pigments, benzimidazolone pigments, disazo condensate pigments, azo pigments, thioindigo pigments, pyrantrone pigments, dioxazine pigments, quinophthalone pigments, isoindoline pigments, phthalocyanine pigments Pigments, etc. are mentioned. Among them, phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and quinacridone pigments are preferable from the viewpoint of more suitably exerting the effects of the present invention. As a phthalocyanine-based pigment, when represented by a color index (C.I.) number, for example, C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, etc. are mentioned. As an anthraquinone pigment, for example, C.I. Pigment Red 177, etc. are mentioned. As a diketopyrrolopyrrole pigment, for example, C.I. Pigment Red 254, 255, 272, 291, etc. are mentioned. As the quinacridone pigment, for example, C.I. Pigment Red 122, 202, 209, etc. are mentioned.

Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, and methine dyes.

The above-mentioned specific pigment derivatives may be used alone or in combination of two or more.

In addition to these specific pigment derivatives, other pigment derivatives may be used in combination. Such other pigment derivatives include, for example, Japanese Patent Laid-Open No. 11-49974, Japanese Patent Laid-Open No. 11-189732, Japanese Patent Laid-Open No. Hei 10-245501, Japanese Patent Laid-Open No. 2006-265528, and Japanese Patents Unexamined Patent Publication No. 8-295810, Unexamined Japanese Patent Publication No. 11-199796, Unexamined Japanese Patent 2005-234478, Unexamined Japanese Patent 2003-240938, Unexamined Japanese Patent 2001-356210, Japanese Patent Those described in Unexamined Publication No. 2007-186681, Unexamined Japanese Patent No. 2003-167112, Unexamined Japanese Patent No. 2013-199470, etc. are mentioned.

The content (solid content) of the pigment derivative in the pigment dispersion is preferably 2 to 15 parts by weight, more preferably 5 to 10 parts by weight, based on 100 parts by weight of the pigment from the viewpoint of improving dispersibility and contrast. However, it is preferable to appropriately adjust the optimal amount of the pigment derivative by combination with the type of pigment and dispersant to be used. In addition, it is the total amount when using another pigment derivative.

The pigment contained in the pigment dispersion may be either an organic pigment or an inorganic pigment, but an organic pigment is preferable. As an organic pigment, when represented by a color index number, the following things are mentioned, for example.

As a red pigment, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41 , 48, 48:1, 48:2, 48:3, 48:4, 48:5, 49, 52, 52:1, 52:2, 53:1, 54, 57:1, 58, 60:1 , 63, 64:1, 68, 81:1, 83, 88, 89, 95, 112, 114, 119, 122, 123, 129, 136, 144, 146, 147, 149, 150, 164, 166, 168 , 169, 170, 171, 172, 175, 176, 177, 178, 179, 181, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210 , 211, 213, 214, 216, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263 , 264, 266, 268, 269, 270, 271, 272, 279, 291, and the like.

As a blue pigment, C.I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17:1, 24, 24:1, 25, 26, 56, 60 , 61, 62, 63, 75, 79, 80, and the like.

As a yellow pigment, C.I. Pigment Yellow 138, 139, 150, 180, 185, etc. are mentioned.

As an orange pigment, C.I. Pigment Orange 43, 71, 73, etc. are mentioned.

As a green pigment, C.I. Pigment Green 1, 4, 7, 8, 10, 36, 58, 59, 63, etc. are mentioned.

As a purple pigment, C.I. Pigment Violet 1, 2, 3, 3:1, 3:3, 5:1, 13, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50, etc. Can be lifted.

Pigments may be used alone or in combination of two or more of the above-described pigments. From the viewpoint of securing good dispersibility, the content of the pigment is preferably 8 to 25% by weight and more preferably 10 to 20% by weight in the pigment dispersion. In addition, the content of the pigment means the total amount with the pigment derivative.

The particle diameter of the pigment can be appropriately determined depending on the application, etc., and those having an average primary particle diameter of approximately 20 to 200 nm, that is, an average primary particle diameter can be preferably used. The average primary particle diameter can be calculated, for example, as an arithmetic average of the maximum width of a plurality of (for example, 50) primary particles being imaged by a transmission electron microscope (TEM).

Depending on the type of pigment, milling treatment may be performed in advance from the viewpoint of improving the contrast, adjusting the average particle diameter, and the like. The milling treatment can be performed according to a method determined according to the type of organic pigment or the like. Examples of such milling treatment include a solvent salt milling method.

As a dispersing agent, a resin type dispersing agent, a surfactant type dispersing agent, etc. are mentioned, for example. As specific examples of the resin type dispersant, for example, polyurethane, polyester, unsaturated polyamide, phosphate, polycarboxylic acid and its amine salt, ammonium salt, alkylamine salt, polycarboxylic acid ester, hydroxyl group-containing polycarboxylic acid Oil-based dispersants such as esters, polysiloxanes, and modified polyacrylates, (meth)acrylic acid-(meth)acrylic acid ester copolymers, (meth)acrylic acid-styrene copolymers, and water-soluble resins or water-soluble polymer compounds such as styrene-maleic acid copolymers Can be lifted.

A resin type dispersant can be used commercially. Specific examples of commercial products are as follows, but are not limited to these.

Japan Lubrizol Co., Ltd.manufacture: Solspur 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000,

Big Chemie Japan Co., Ltd. Manufacturing: Disperbyk 108, 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2050, 2070, 2150, LPN6919, LPN22101, LPN21116,

Manufactured by BASF: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244,

Ajinomoto Fine Techno Co., Ltd.manufacture: Azispur-PB821(F), PB822, PB880,

Kawaken Fine Chemical Co., Ltd.: Hinoact T-8000,

Manufactured by Kusumoto Hwaseong Co., Ltd.: Dispalon PW-36, Dispalon DA-325, 375, 7301,

Otsuka Chemical Co., Ltd.manufacture: TERPLUS D2015, etc.

The molecular weight of the resin type dispersant can be appropriately selected in consideration of the characteristics of each component. For example, a weight average molecular weight of 1000 to 100000 can be used.

Surfactant-type dispersants include naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, anionic activators such as polyoxyethylene alkyl phosphate, nonionic activators such as polyoxyethylene alkyl ether, alkylamine salts, quaternary ammonium salts, etc. And cationic activators.

A commercially available surfactant type dispersant can be used. Specific examples of commercial products are as follows, but are not limited to these.

Made by Kao Corporation: Demol N, RN, MS, SN-B, Emulgen 120, 430, Acetamine 24, 86, Cotamine 24P,

Nikko Chemicals Co., Ltd.: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25,

Daiichi Industrial Pharmaceutical Co., Ltd.manufacture: Flysurf AL, A208F,

Manufactured by Lion Corporation: Acard C-50, T-28, T-50, etc.

One type or two or more types of dispersants may be contained. The content (solid content or active ingredient) of the dispersant is preferably 10 to 40 parts by weight based on 100 parts by weight of the total of the pigment and the pigment derivative from the viewpoint of ensuring good dispersibility. However, the optimum amount of the dispersant to be added is preferably adjusted appropriately by a combination with the type of pigment to be used.

In the pigment dispersion, from the viewpoint of further improving the dispersibility of pigments, etc., a dispersion resin may be used as a dispersion aid. Such a dispersion resin is particularly suitable to be used when the coating film forming component described later contains a polymerizable component, particularly a photopolymerizable component. Before adding the polymerizable component, by preparing a pigment dispersion containing a dispersion resin, a pigment, a pigment derivative, a dispersant, and a solvent, the dispersibility of each solid component when the polymerizable component is added becomes good. As such a dispersion resin, an alkali-soluble resin mentioned later is mentioned. The dispersion resin may be of the same type as the alkali-soluble resin used as a coating film forming component, or may be a different type of resin. The content of the dispersion resin is preferably 10 to 50 parts by weight based on 100 parts by weight of the total of the pigment and the pigment derivative.

The solvent can be appropriately selected according to the kind of the coating film forming component described later, and examples thereof include various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic. Among them, from the viewpoint of coating film formation, an organic solvent selected from aromatic, ketone, ester, and glycol ether is preferred. The organic solvent may be one type or a combination of two or more.

As an aromatic organic solvent, aromatic hydrocarbons, such as toluene, xylene, and ethylbenzene, are mentioned, for example.

Examples of ketone-based organic solvents include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

Examples of ester-based organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate (PMA ), propylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butylcarbitol acetate, butyl lactate , Ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butylene glycol diacetate, and the like.

As a glycol ether organic solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether , Ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether , Propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso- Water-soluble glycol ethers such as propyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-n-butyl ether,

Ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl Water-insoluble glycol ethers, such as ether, dipropylene glycol propyl ether, and propylene glycol methyl ether propionate, etc. are mentioned.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, and isopropanol,

Ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, Tripropylene glycol, polyethylene glycol with a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6- Hexanediol, glycerin, mesoerythritol, pentaerythritol, etc. are mentioned.

As an aliphatic organic solvent, an aliphatic hydrocarbon, such as n-pentane, n-hexane, n-heptane, etc. are mentioned, for example.

The amount of the solvent to be added can be added so that the solid content concentration including the pigment or the like is 10 to 30% by weight in the pigment dispersion from the viewpoint of handling properties.

In the embodiment of the pigment dispersion of the present invention, other additives may be included in addition to the above-described components. As another additive, an antioxidant, an anti-aggregation agent, a surface adjuster (leveling agent), etc. are mentioned.

The pigment dispersion can be obtained, for example, by adding and dispersing each of the aforementioned components to a known dispersing machine such as a bead mill, sand mill, or disper. The method of adding each component is not particularly limited, and the mixture of each component at the same time may be subjected to dispersion treatment.For example, in the case of using a plurality of pigments, a dispersion may be prepared in advance for each pigment, and then a dispersion treatment may be performed again. .

The coloring composition for coating film formation according to the embodiment of the present invention (hereinafter, sometimes referred to as "coloring composition") contains the above-described pigment dispersion and coating film-forming component. In this way, since a specific pigment dispersion is contained, the coating film obtained by using the coloring composition for forming a coating film has good contrast.

Examples of the coating film forming component include a polymerizable component, a polymer, and a mixture thereof.

Examples of the polymer include thermoplastic urethane resins, (meth)acrylic resins, polyamide resins, polyimide resins, styrene maleic acid resins, polyester resins, silicone resins, cardo resins, and the like.

The content of the polymer in the colored composition is preferably 10 to 40% by weight, and more preferably 20 to 30% by weight, based on the total solid content of the colored composition. It is the total amount when it is contained also as a dispersion resin in a pigment dispersion. The molecular weight of the polymer can be appropriately determined.

Among the polymers described above, alkali-soluble resins exhibiting solubility in solutions in the alkali region are preferred.

When an alkali-soluble resin is contained, for example, in a photolithography process at the time of manufacturing a color filter, when a pigment composition is applied to pattern formation, pattern formation can be improved more.

As such an alkali-soluble resin, those described in Japanese Patent Laid-Open No. 2009-179789 can be used, for example. Briefly, the alkali-soluble resin is, for example, a linear organic high-molecular polymer, and at least one group promoting alkali solubility in the molecule (preferably, a molecule having an acrylic copolymer or a styrene-based copolymer as a main chain) (e.g., It can be appropriately selected from alkali-soluble resins having a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Among them, more preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

The weight average molecular weight of the alkali-soluble resin is preferably 5000 to 500,000 from the viewpoint of developability.

Various alkali-soluble resins are commercially available, and specific examples thereof are as follows, but are not limited thereto.

Showa Polymer Co., Ltd.: Lipoxy SPC-2000,

Mitsubishi Rayon Co., Ltd. manufacturing: Diamond NR series,

Diamond hamrock Co. Ltd., Manufacture: Photomer6173 (Polyurethane acrylic oligomer containing COOH),

Osaka Organic Chemical Industry Co., Ltd.manufacture: Viscoat R-264, KS resist 106, SOP-005,

Daicel Chemical Industry Co., Ltd.: Cyclomer P series, Flaxel CF200 series,

Daicel UCB Co., Ltd.: Ebecryl 3800,

Nippon Shokubai Co., Ltd.: Aclique (registered trademark) RD-Y-503, RD-Y-702-A, BX-Y-10, etc.

As the polymerizable component, a photopolymerizable component is preferred because it is easy to perform patterning by development (negative development).

The photopolymerizable component that can be used includes a photopolymerizable compound and a photopolymerization initiator. Such photopolymerizable compounds and photopolymerization initiators can be used, for example, those described in Japanese Patent Laid-Open No. 2009-179789. In detail, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. These groups of compounds are widely known in the above technical field, and they can be used without particular limitation in the present invention. The photopolymerizable compound has, for example, a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of the monomer and its copolymer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, and preferred Preferably, esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound are used. In addition, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, or an addition reaction product of an amide and a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional carboxyl Dehydration and condensation reaction products with acids are also suitably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, and thiols, and leaving substituents such as halogen or tosyloxy groups Substitution reaction products of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, as another example, instead of the unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, or the like may be used.

The photopolymerizable compound is contained in an amount of preferably 5 to 70% by weight, more preferably 10 to 60% by weight, based on the nonvolatile component in the coloring composition. In addition, these may be used alone or in combination of two or more. In addition, the use of the photopolymerizable compound can be arbitrarily selected from the viewpoint of the size, resolution, cloudiness, refractive index change, and surface adhesion of the polymerization inhibition to oxygen.

As the photopolymerization initiator, for example, those described in Japanese Patent Laid-Open No. 2009-179789 can be used.

For example, acetophenone-based, ketal-based, benzophenone-based, benzoin-based, benzoyl-based, xanthone-based, active halogen compound (triazine-based, oxadiazole-based, coumarin-based), acridine-based, biimidazole-based, oxime ester-based, etc. to be.

Specific examples of these are benzophenone-based photopolymerization initiators, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4 And 4'-dichlorobenzophenone.

The content of the photopolymerization initiator in the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total solid content of the colored composition. When the content of the photopolymerization initiator is within this range, the polymerization reaction proceeds satisfactorily and a film with good strength can be formed.

When the coloring composition contains a photopolymerizable component as a coating film forming component, the alkali-soluble resin described above may be contained.

In the coloring composition, if necessary, a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a surfactant, an adhesion promoter, an antioxidant, an anti-aggregation agent, a surface adjuster (leveling agent). Various additives such as may be added.

The coloring composition can be obtained, for example, by adding and dispersing each of the aforementioned components to a known dispersing machine such as a bead mill, sand mill, or disper.

The above-described colored composition has good dispersibility, and a coating film obtained by using this can have a good contrast. Therefore, the colored composition can be favorably applied to a color filter widely used as a constituent member such as a liquid crystal display (LCD) or an organic electroluminescent (EL) display.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail based on Examples.

(Production Example 1): Preparation of pigment derivative 1

Concentrated sulfuric acid (98%): After cooling the liquid temperature of 1000 g to 10°C, diketopyrrolopyrrole (DPP) pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, CI Pigment Red 255): 28.8 g (100 mmol) ), paraformaldehyde: 1.9 g, 1-(3'-sulfophenyl)-3-methyl-5-pyrazolone (3PY): 16.4 g were added. Then, it heated up to 55 degreeC and stirred at this temperature for 3 hours. The reaction solution was discharged to 2 L of cold water, and filtered with suction and washed with ion-exchanged water. The obtained water paste: 186 g was dried at 80 DEG C for 20 hours to obtain a pigment derivative 1: 36.4 g.

In the negative mode spectrum obtained by MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corporation) and using 2,5-dihydroxybenzoic acid (DHBA) as a matrix, the target product (m/ z=544). That is, it was confirmed that the pigment derivative 1 contained the compound represented by the formula (1) (the pigment residue Q is the residue of the DPP pigment, and X is the methylene group).

(Production Example 2): Preparation of pigment derivative 2

In the same manner as in Preparation Example 1, except for using BASF, Irgazin Scaret L 3550 HD, BASF, Irgazin Frame Red K 3800 (diketopyrrolopyrrole (DPP) pigment, CI pigment red 272) Derivative 2: 34.3 g was obtained. In the same manner as in Production Example 1, it was confirmed that the target product (m/z=582) had a peak in the negative mode spectrum using DHBA as the matrix. That is, it was confirmed that the pigment derivative 2 contained the compound represented by the formula (1) (the pigment residue Q is the residue of the DPP pigment, and X is the methylene group).

(Production Example 3): Preparation of pigment derivative 3

Concentrated sulfuric acid (98%): After cooling 150 g of liquid temperature to 10°C, DPP pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, CI Pigment Red 255): 8.65 g (30.0 mmol), 4-aminop Deimide: 6.1 g, paraformaldehyde: 1.2 g were added. After heating up to 27.5 degreeC, it stirred at this temperature for 1 hour. This reaction solution was discharged into cold water: 0.6 L. Ice was added to bring the sulfuric acid concentration to about 20% and cooled to 0°C or less. A sodium nitrite aqueous solution: 7.0 g (8.0 mol/L) was slowly added dropwise thereto, followed by stirring at 5°C or lower for 1 hour to obtain a diazotized solution.

To the ion-exchanged water: 103 g, a 30% aqueous sodium hydroxide solution: 8.4 g and 3PY: 8.3 g were added and dissolved. Further, 50% aqueous sodium acetate solution: 813 g was added, and the liquid temperature was adjusted to 20°C. The pH at this time was 11.2. Here, the diazotization liquid was dripped from the dropping lot. The pH after dropping was 3.9. After stirring at 20°C for 1 hour, the temperature was raised to 60°C, followed by stirring at this temperature for 1 hour. After the reaction, the reaction solution was cooled to 50° C., and then filtered with suction to pH<2 with 35% hydrochloric acid. The filtrate was washed with 5 L of ion-exchanged water and dried at 80°C to obtain a pigment derivative 3: 20.9 g.

In the same manner as in Production Example 1, it was confirmed that the target product (m/z=729) had a peak in the negative mode spectrum using DHBA in the matrix. That is, the obtained pigment derivative 3 is a compound represented by formula (1) (a pigment residue Q is a residue of a DPP pigment, X is a linking group represented by a formula (1-2), and * in formula (1-2) It was confirmed that the displayed connecting hand was the Q side).

(Production Example 4): Preparation of pigment derivative 4

DPP pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, CI Pigment Red 255) in 630 g of concentrated sulfuric acid (98%): 35.0 g (121 mmol) and paraformaldehyde: 4.50 g and 4-aminophthalimide : 24.7 g was added and reacted at 30°C for 5 hours. Next, this reaction solution was discharged to 3 L of cold water, filtered and washed with water, to which one 4-aminophthalimide methyl group was introduced into the water of the 4-aminophthalimide methyl DPP pigment derivative. Paste: 400 g (solid content: 11.2%) was obtained.

Next, water: 90.0 g, ortanylic acid: 3.90 g and sodium carbonate: 1.20 g were added and dissolved, and cooled to 5°C or less. To this, cyanuric chloride: 4.20 g was added and reacted at 5°C for 1 hour. Next, a water paste of the DPP-based pigment derivative into which one 4-aminophthalimide methyl group was introduced: 58.0 g (solid content: 11.2%) was added, and reacted at 85° C. for 1 hour. After the reaction, it was filtered with suction and washed with ion-exchanged water. The obtained water paste: 86.0 g was dried at 100° C. for 20 hours to obtain a pigment derivative 4: 8.03 g having the structure of the following formula (2). In the same manner as in Production Example 1, it was confirmed that the target product (m/z=728) had a peak in the negative mode spectrum using DHBA as the matrix.

(Production Example 5): Preparation of pigment derivative 5

Pigment derivative 5 in the same manner as in Preparation Example 1 except for using BASF, Irgazin Scaret L 3550 HD, Zhuhai Dongyang Color Materials Co., Ltd., T-99 CRUDE BLUE (phthalocyanine pigment, CI pigment blue 15). : 74.3 g was obtained. In the same manner as in Production Example 1, it was confirmed that the target product (m/z = 840) had a peak in the negative mode spectrum using DHBA as the matrix. That is, it was confirmed that the pigment derivative 5 contained the compound represented by the formula (1) (the pigment residue Q is a residue of a phthalocyanine pigment, and X is a methylene group).

(Production Example 6): Preparation of pigment derivative 6

78% sulfuric acid: To 175 g, Cinic Corporation make, Cinilex Red SR3C (anthraquinone pigment, C.I. Pigment Red 177): 22.2 g (50.0 mmol) was added. After cooling to 0°C or less, sodium nitrite aqueous solution: 23.3 g (8.0 mol/L) was slowly added dropwise, followed by stirring at 5°C or less for 1 hour to obtain a diazotized solution. Ion-exchanged water: 360 g of 30% sodium hydroxide aqueous solution: 28.0 g and 3PY: 28.6 g were added and dissolved. Further, 50% aqueous sodium acetate solution: 600 g was added, and the liquid temperature was adjusted to 20°C. Here, the diazotized liquid was dripped from the dropping lot. The pH after dropping was 4.4. After stirring at 20 degreeC for 1 hour, it heated up to 60 degreeC, and stirred at this temperature for 1 hour. After the reaction, the reaction solution was cooled to 50° C., and the pH was adjusted to <2 with 35% hydrochloric acid, followed by suction filtration. The filtrate was washed with 3 L of ion-exchanged water and dried at 80°C to obtain a pigment derivative 6: 48.1 g.

In the same manner as in Production Example 1, it was confirmed that the target product (m/z=709) had a peak in the negative mode spectrum using DHBA in the matrix. That is, it was confirmed that the pigment derivative 6 contained the compound represented by the formula (1) (the pigment residue Q is the residue of the anthraquinone pigment, and X is the azo group).

(Production Example 7): Preparation of pigment derivative 7

The structure of the following formula (3) was carried out in the same manner as in Production Example 4, except that the production of BASF, instead of Irgazin Scaret L 3550 HD, was used by Cinic, Cinilex Red SR3C (anthraquinone pigment, CI pigment red 177). Pigment derivative 7: 42.8 g was obtained. In the same manner as in Production Example 1, it was confirmed that the target product (m/z=884) had a peak in the negative mode spectrum using DHBA as the matrix.

(Production Example 8): Preparation of pigment derivative 8

Pigment derivative 8: 22.6 in the same manner as in Preparation Example 3 except for using BASF, IRGAZIN DPP Scaret EK, DIC Corporation, Fastogen Super RED 209 228-6736 (quinacridone pigment, CI pigment red 209). g. In the same manner as in Production Example 1, it was confirmed that the target product (m/z=820) had a peak in the negative mode spectrum using DHBA as the matrix. That is, the pigment derivative 8 is a compound represented by formula (1) (a pigment residue Q is a residue of a quinacridone pigment, X is a linking group represented by a formula (1-2), and * in formula (1-2) It was confirmed that the displayed connecting hand was the Q side).

The components shown in Table 1 used in the following Examples and Comparative Examples are as follows. In addition, the components indicated in Table 1 are shown in parentheses.

<Pigment>

1) C.I. Pigment Blue 15:6 (PB 15:6)

FASTOGEN Blue EP-207, manufactured by DIC Corporation

2) C.I. Pigment Red 254 (PR 254)

Iragzin (registered trademark) Red L3630, manufactured by BASF

3) C.I. Pigment Yellow 139 (PY 139)

Iragzin (registered trademark) Yellow S2150CF, manufactured by BASF

4) C.I. Pigment Red 209 (PR 209)

Fastogen Super RED 209 228-6736, manufactured by DIC Corporation

<Dispersant>

1) Disperbyk LPN6919 (LPN6919), manufactured by Big Chemie Japan

2) Disperbyk LPN21116 (LPN21116), manufactured by Big Chemie Japan Co., Ltd.

<Dispersion resin>

SPC-2000 (SPC2000), manufactured by Showa Denko Co., Ltd.

<Pigment derivative>

Solspur 12000 (Solspur), manufactured by Lubrizol, Japan

<solvent>

Propylene glycol monomethyl ether acetate (PMA), manufactured by Kyowa Fermentation Chemical Co., Ltd.

(Examples 1 to 6, Comparative Examples 1 to 4)

<Preparation of pigment dispersion>

A pigment derivative, a pigment, a dispersant, a dispersion resin, and a solvent were added to the sand mill so that the composition as shown in Table 1 might be obtained. After stirring for 10 minutes at 2000 rotations, 800 g of φ0.5 mm zirconia beads were added, and dispersion treatment was performed at 2000 rotations for 2 hours. Thereafter, the zirconia beads were removed to obtain pigment dispersions 1 to 10. In addition, in Comparative Example 4, instead of the pigment derivative, Pigment Red 209, which is a raw material pigment of Production Example 8, was used. In addition, the unit of the component composition in Table 1 is weight%.

<Preparation of the coloring composition for coating film formation>

Alkali-soluble resin (manufactured by Nippon Shokubai Co., Ltd., Acliqueur (registered trademark) BX-Y-10, acrylic polymer): 12.0% by weight, polyfunctional acrylate monomer (dipentaerythritol (hexa/penta) acrylic as a photopolymerizable component) Rate, Nihon Kayaku Co., Ltd. make, KAYARAD DPHA): 26.0% by weight, a photopolymerization initiator (BASF Japan, Irgacure369): 4.0% by weight, PMA as a solvent: 58.0% by weight of the coating film forming component was prepared.

The obtained pigment dispersions 1 to 10: 6.0 g and coating film forming component: 4.0 g were mixed and stirred with a disper to obtain a colored composition for forming a coating film.

<Evaluation>

<<<Viscosity of pigment dispersion>>

The viscosity immediately after preparation of the obtained pigment dispersions 1-10 was measured using the Toki Industries make, E-type viscometer "RE-80L". Table 1 shows the measurement results.

<<Contrast of coating>>

In the case of the colored composition for forming a blue coating film prepared in Example 4 and Comparative Example 2, the chromaticity was y=0.107, and in the case of the colored composition for forming a red coating film prepared in other Examples and Comparative Examples, the chromaticity x= Using a spin coater (manufactured by Mika Corporation, spin coater MS-150A) adjusted to a rotation speed of 0.648, the colored composition for coating film formation obtained as described above was applied to a glass plate having a thickness of 1 mm and a width of 100 mm. did. After allowing this coating plate to stand at room temperature for 5 minutes, it was dried (prebaked) by airbus at 80°C for 2 minutes. In addition, using an exposure device (manufactured by Sanei Electric Co., Ltd., brand name: UVE-1001S type exposure light source device, YSH-100SA type ultra-high pressure mercury lamp), ultraviolet rays (UV) are applied to the coating plate to achieve an exposure intensity of 60 mJ/cm 2. It irradiated and post-baked at 235 degreeC for 30 minutes. The post-baked coating plate was sandwiched between a polarizing plate (trade name: POLAX-38S, manufactured by Lukeo Corporation) on a lamp (brand name: HF-LS-100WLCG). The luminance when the polarizing plate is in the position of Cross Nicol and the luminance when the polarizing plate is in the parallel position are measured using a color luminance meter (brand name: LS-100, manufactured by Konica Minolta Sensing Co., Ltd.), and the ratio ( %) was calculated as the contrast (CR). Values were shown in Examples 1 to 3 in Comparative Example 1, and in Examples 4 to 6 as ratios to Comparative Examples 2 to 4, respectively. Table 1 shows the results.

As shown in Table 1, from the comparison between Examples 1 to 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, by using a specific pigment derivative , It can be seen that the dispersibility of the pigment dispersion is good, and the contrast of the coating film is improved.

Claims (5)

A pigment dispersion containing at least one pigment derivative, a pigment, a dispersant, and a solvent selected from compounds represented by the following formula (1).

(In formula (1), Q represents a dye residue, X represents a methylene group (-CH ₂ -), an azo group (-N=N-), or a linking group represented by the following formula (1-2).)

(In formula (1-2), * and ** represent a bonded hand.) The pigment dispersion according to claim 1, wherein Q in formula (1) is a residue of a pigment. The pigment dispersion according to claim 2, wherein Q in formula (1) is a residue of a pigment selected from a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, and a quinacridone pigment. A coloring composition for forming a coating film comprising the pigment dispersion according to any one of claims 1 to 3 and a coating film forming component. The coloring composition for coating film formation according to claim 4, comprising a photopolymerizable component as the coating film-forming component.