JP7369371B2 - Pigment dispersion and coloring composition for coating film formation - Google Patents

Description

The present invention relates to a pigment dispersion and a coloring composition for forming a coating film, and particularly to a pigment dispersion and a coloring composition for forming a coating film that can be applied to a color filter of an image display device.

Color filters are widely used as constituent members of, for example, liquid crystal displays (LCDs) and organic electroluminescent (EL) displays. For example, LCDs are widely used in display devices such as monitors, televisions, notebook computers, tablet computers, and smartphones. These display devices are required to have higher image quality. Therefore, the color filters that make up these devices are required to have high contrast.

Color filters are manufactured by forming a coating film through a photolithography process using a colored photosensitive composition in which colorants such as red, green, and blue dyes and pigments are dissolved or dispersed in a photosensitive resin as a coating solution. It is widely practiced. As described above, one possible method for improving the image quality of color filters is to improve color purity by increasing the concentration of dyes and pigments in the colored photosensitive composition. Furthermore, in order to achieve high contrast, it is conceivable to eliminate large pigment particles and disperse the pigment in the colored photosensitive composition as small particles having a diameter equal to or less than the wavelength of light. However, the smaller the particle size of the pigment, the more likely it is to aggregate and the higher its viscosity, making it difficult to uniformly disperse it in a colored photosensitive composition.

Therefore, as a countermeasure to this problem, it is widely practiced to improve the dispersibility of particles in the composition by using pigment derivatives or dispersants in which functional groups such as acidic groups are introduced into dyes such as pigments. (Patent Document 1). Patent Document 1 discloses that an isoindoline derivative having a specific pyrazolone skeleton, which is a sulfonic acid or its metal salt or quaternary ammonium salt, which is composed of indoline and barbiturate moieties, is used as a dispersant, thereby dispersing isoindoline and barbiturate moieties. In a pigment composition using a yellow pigment having a structure based on tool acid, fine particles can be formed in the dispersion composition without causing high viscosity immediately after dispersion, agglomeration, sedimentation, or an increase in viscosity over time. It is described that it is possible to increase the concentration and provide a stable pigment composition as a coloring agent for color filter resists and inkjet inks.

However, even with the use of such dispersants, the current situation is that the demand for high-image quality display devices in the market cannot be fully met.

Japanese Patent Application Publication No. 2009-120777

An object of the present invention is to provide a pigment dispersion that has good dispersibility and can realize a high-contrast color filter, and a coloring composition for forming a coating film containing the same.

The present inventor conducted extensive studies to solve the above-mentioned problem. As a result, it has been found that the above-mentioned problems can be solved by using a pigment derivative with a specific structure.

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

(In formula (1), Q represents a dye residue, and 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 ** indicate bonds.)

In an 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 phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and quinacridone pigments.

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

In an embodiment of the present invention, the coating film forming component may include a photopolymerizable component.

According to the present invention, it is possible to provide a pigment dispersion that has good dispersibility and can realize a high-contrast color filter, and a coloring composition for forming a coating film containing the same.

Embodiments of the present invention will be described below.

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

(In formula (1), Q represents a dye residue, and 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 ** indicate bonds.)

By using such a specific pigment derivative, it is possible to prevent particles in the pigment dispersion from agglomerating, thereby preventing an increase in viscosity. Further, the contrast of a coating film obtained using a coloring composition for forming a coating film containing a pigment dispersion can be improved more than before. Although the reason for this is not necessarily clear, it is presumed that the arrangement of dispersed particles in the coating film has approached a state in which it is relatively difficult to scatter light.

The pigment derivative may be any compound represented by formula (1). When the linking group However, from the viewpoint of better exerting the effects of the present invention, it is preferable that the connecting hand on the side indicated by * be connected to the dye residue Q.

The dye that forms the basis of the dye residue Q may be either a pigment or a dye. The pigment is preferably an organic pigment, such as anthraquinone pigments, aminoanthraquinone pigments, quinacridone pigments, quinacridonequinone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, anthoanthrone pigments, benzene pigments, etc. Examples include imidazolone pigments, disazo condensate pigments, azo pigments, thioindigo pigments, pyranthrone pigments, dioxazine pigments, quinophthalone pigments, isoindoline pigments, and phthalocyanine pigments. Among these, phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and quinacridone pigments are preferred from the viewpoint of more suitably exhibiting the effects of the present invention. Examples of phthalocyanine pigments include C.I. I. Pigment Blue 15, 15:3, 15:4, 15:6, 16 and the like. Examples of anthraquinone pigments include C.I. I. Pigment Red 177 and the like. Examples of diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 272, 291 and the like. Examples of quinacridone pigments include C.I. I. Pigment Red 122, 202, 209 and the like.

Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, methine dyes, and the like.

One type of the above-mentioned specific pigment derivative may be used, or two or more types may be used.

In addition to such specific pigment derivatives, other pigment derivatives may be used in combination. Examples of such other pigment derivatives include, for example, JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, and JP-A-8-295810. Publication, JP 11-199796, JP 2005-234478, JP 2003-240938, JP 2001-356210, JP 2007-186681, JP 2003-167112, Examples include those described in JP-A No. 2013-199470.

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 dispersibility and contrast improvement. However, the optimum amount of the pigment derivative to be added may be adjusted as appropriate depending on the combination of the pigment and the type of dispersant used. In addition, when using other pigment derivatives, the amount is the total amount.

The pigment contained in the pigment dispersion may be either an organic pigment or an inorganic pigment, but an organic pigment is preferred. Examples of organic pigments include the following in terms of color index numbers.

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, etc.

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, etc.

As a yellow pigment, C. I. Pigment Yellow 138, 139, 150, 180, 185 and the like.

As the orange pigment, C. I. Pigment Orange 43, 71, 73, etc.

As a green pigment, C. I. Pigment Green 1, 4, 7, 8, 10, 36, 58, 59, 63 and the like.

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 mentioned.

As the pigment, the above-mentioned pigments can be used alone or in combination of two or more. From the viewpoint of ensuring good dispersibility, the pigment content in the pigment dispersion is preferably 8 to 25% by weight, more preferably 10 to 20% by weight. Incidentally, the pigment content means the total amount including the pigment derivative.

The particle size of the pigment can be determined as appropriate depending on the intended use, etc., and it is preferable to use one whose average primary particle size, that is, the average primary particle size, is approximately 20 to 200 nm. The average primary particle diameter can be calculated, for example, as the arithmetic average of the maximum widths 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 contrast, adjusting the average particle diameter, etc. The milling treatment can be carried out according to a conventional method depending on the type of organic pigment, etc. Examples of such milling treatment include solvent salt milling and the like.

Examples of the dispersant include resin-type dispersants, surfactant-type dispersants, and the like. Specific examples of resin-type dispersants include polyurethane, polyester, unsaturated polyamide, phosphoric acid ester, polycarboxylic acid and its amine salts, ammonium salts, and alkyl amine salts, polycarboxylic acid esters, hydroxyl group-containing polycarboxylic acid esters, and polycarboxylic acid esters. Oil-based dispersants such as siloxane and modified polyacrylate, water-soluble resins such as (meth)acrylic acid-(meth)acrylic acid ester copolymer, (meth)acrylic acid-styrene copolymer, and styrene-maleic acid copolymer and water-soluble polymer compounds.

Commercially available resin-type dispersants can be used. Specific examples of commercially available products are as follows, but are not limited thereto.
Made by Japan Lubrizol Co., Ltd.: Solsperse 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000,
Byk Chemie Japan Co., Ltd.: 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,
Manufactured by Ajinomoto Fine Techno Co., Ltd.: Ajisper-PB821 (F), PB822, PB880,
Manufactured by Kawaken Fine Chemicals Co., Ltd.: Hinoact T-8000,
Manufactured by Kusumoto Kasei Co., Ltd.: Disparon PW-36, Disparon DA-325, 375, 7301,
Manufactured by Otsuka Chemical Co., Ltd.: 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, those having a weight average molecular weight of 1,000 to 100,000 can be used.

Examples of surfactant-type dispersants include naphthalene sulfonic acid formalin condensates, aromatic sulfonic acid formalin condensates, anionic activators such as polyoxyethylene alkyl phosphates, nonionic activators such as polyoxyethylene alkyl ethers, and alkyl amines. Examples include cationic activators such as salts and quaternary ammonium salts.

Commercially available surfactant-type dispersants can be used. Specific examples of commercially available products are as follows, but are not limited thereto.
Manufactured by Kao Corporation: Demol N, RN, MS, SN-B, Emulgen 120, 430, Acetamine 24, 86, Cortamine 24P,
Manufactured by Nikko Chemicals Co., Ltd.: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25,
Daiichi Kogyo Seiyaku Co., Ltd.: Pricesurf AL, A208F,
Manufactured by Lion Corporation: Alucard C-50, T-28, T-50, etc.

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

In the pigment dispersion, a dispersion resin may be used as a dispersion aid from the viewpoint of further improving the dispersibility of pigments and the like. Such a dispersion resin is particularly suitable for use when the coating film forming component described below contains a polymerizable component, particularly a photopolymerizable component. By preparing a pigment dispersion containing a dispersion resin, pigment, pigment derivative, dispersant, and solvent before adding the polymerizable component, the dispersibility of each solid content when the polymerizable component is added is improved. . Examples of such dispersion resins include alkali-soluble resins described below. The dispersed resin may be the same type of resin as the alkali-soluble resin used as the 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 the total of 100 parts by weight of the pigment and pigment derivative.

The solvent can be selected as appropriate depending on the type of coating film-forming component described below, and includes various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic solvents. can be mentioned. Among these, from the viewpoint of film forming properties, organic solvents selected from aromatic, ketone, ester, and glycol ether solvents are preferred. The organic solvent may be used alone or in combination of two or more.

Examples of aromatic organic solvents include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

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

Examples of ester 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, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypro Examples include pionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, and 1,3-butylene glycol diacetate.

Examples of glycol ether organic solvents include 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, and 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 Water-soluble ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, etc. glycol ethers,
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 ether, dipropylene glycol propyl ether, Examples include water-insoluble glycol ethers such as propylene glycol methyl ether propionate.

Examples of alcohol-based organic solvents 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 and the like.

Examples of aliphatic organic solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

From the viewpoint of ease of handling, the amount of solvent to be added can be such that the concentration of solids containing pigment etc. in the pigment dispersion is 10 to 30% by weight.

Embodiments of the pigment dispersion of the present invention may contain other additives in addition to the components described above. Other additives include antioxidants, anti-aggregation agents, surface conditioners (leveling agents), and the like.

The pigment dispersion can be obtained, for example, by adding each of the above-mentioned components to a known dispersion machine such as a bead mill, sand mill, or disper, and dispersing the dispersion. There is no particular limitation on how each component is added; each component may be mixed at the same time and then subjected to dispersion treatment. For example, if multiple types of pigments are used, a dispersion for each pigment is prepared in advance and then mixed. Then, the distributed processing may be performed again.

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

Examples of the coating film-forming component include polymerizable components, polymers, and mixtures thereof.

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

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

Among the above-mentioned polymers, alkali-soluble resins that exhibit solubility in solutions in the alkaline region are preferred.

When the pigment composition contains an alkali-soluble resin, pattern forming properties can be further improved when the pigment composition is applied to pattern formation in, for example, a photolithography process during the production of color filters.

As such alkali-soluble resin, those described in JP-A No. 2009-179789 can be used. Briefly, the alkali-soluble resin is, for example, a linear organic polymer, and the molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as its main chain) contains at least It can be appropriately selected from alkali-soluble resins having one group that promotes alkali solubility (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Among these, those that are soluble in organic solvents and developable with weak alkaline aqueous solutions are more preferred.

The weight average molecular weight of the alkali-soluble resin is preferably 5,000 to 50,000 from the viewpoint of developability.

Various alkali-soluble resins are commercially available, and specific examples thereof are as follows, but the invention is not limited thereto.
Showa Kobunshi Co., Ltd.: Lipoxy SPC-2000,
Manufactured by Mitsubishi Rayon Co., Ltd.: Dianal NR series,
Diamond hamrock Co. Ltd. , manufactured by: Photomer6173 (COOH-containing polyurethane acrylic oligomer),
Osaka Organic Chemical Industry Co., Ltd.: Viscoat R-264, KS Resist 106, SOP-005,
Daicel Chemical Industries, Ltd.: Cyclomer P series, Plaxel CF200 series,
Manufactured by Daicel UCB Corporation: Ebecryl 3800,
Nippon Shokubai Co., Ltd.: AcryCure (registered trademark) RD-Y-503, RD-Y-702-A, BX-Y-10, etc.

As the polymerizable component, a photopolymerizable component is preferable because patterning can be easily performed by development (negative development).

Usable photopolymerizable components include photopolymerizable compounds and photopolymerization initiators. As such a photopolymerizable compound and a photopolymerization initiator, for example, those described in JP-A No. 2009-179789 can be used. Specifically, such a photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. selected from. Such compound groups are widely known in the technical field, and can be used in the present invention without particular limitation. Photopolymerizable compounds have chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. For example, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds are used. Additionally, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, as well as halogen groups and Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as , tosyloxy group, and monofunctional or polyfunctional alcohols, amines, and thiols. Furthermore, as another example, it is also possible to use a group of compounds in which unsaturated phosphonic acid, styrene, vinyl ether, etc. are substituted for the unsaturated carboxylic acid mentioned above.

The photopolymerizable compound is preferably contained in an amount of 5 to 70% by weight, more preferably 10 to 60% by weight, based on the nonvolatile components in the coloring composition. Further, these may be used alone or in combination of two or more. In addition, the photopolymerizable compound can be used by selecting an appropriate structure, formulation, and amount added from the viewpoints of the degree of inhibition of polymerization by oxygen, resolution, fogging property, change in refractive index, surface tackiness, and the like.

As the photopolymerization initiator, those described in JP-A No. 2009-179789 can be used.
Examples include acetophenone type, ketal type, benzophenone type, benzoin type, benzoyl type, xanthone type, active halogen compound (triazine type, oxadiazole type, coumarin type), acridine type, biimidazole type, oxime ester type, etc.
Specific examples of these benzophenone photopolymerization initiators include benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'- Examples include dichlorobenzophenone.

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

The coloring composition may contain the above-mentioned alkali-soluble resin when it contains a photopolymerizable component as a coating film-forming component.

The coloring composition may contain, 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, and an oxidizing agent. Various additives such as inhibitors, anti-agglomeration agents, and surface conditioners (leveling agents) may be added.

The colored composition can be obtained, for example, by adding the above-mentioned components to a known dispersion machine such as a bead mill, sand mill, or dispersion machine and dispersing the components.

The coloring composition as described above has good dispersibility, and a coating film obtained using the same can have good contrast. Therefore, the colored composition can be favorably applied to color filters that are widely used as constituent members of liquid crystal displays (LCDs), organic electroluminescence (EL) displays, and the like.

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

(Production Example 1): Production of Pigment Derivative 1 After cooling the liquid temperature of 1000 g of concentrated sulfuric acid (98%) to 10°C, a diketopyrrolopyrrole (DPP) pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, C.I. Pigment Red 255): 28.8 g (100 mmol), paraformaldehyde: 1.9 g, and 1-(3'-sulfophenyl)-3-methyl-5-pyrazolone (3PY): 16.4 g. did. Thereafter, the temperature was raised to 55° C. and stirred at this temperature for 3 hours. This reaction solution was discharged into 2 L of cold water, filtered under suction, and washed with ion-exchanged water. 186 g of the obtained water paste was dried at 80° C. for 20 hours to obtain 36.4 g of pigment derivative 1.

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

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

(Production Example 3): Production of Pigment Derivative 3 After cooling the liquid temperature of 150 g of concentrated sulfuric acid (98%) to 10°C, DPP pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, C.I. Pigment Red) 255): 8.65 g (30.0 mmol), 4-aminophthalimide: 6.1 g, and paraformaldehyde: 1.2 g. After raising the temperature to 27.5°C, the mixture was stirred at this temperature for 1 hour. This reaction solution was drained into 0.6 L of cold water. Ice was added to make the sulfuric acid concentration about 20%, and the mixture was cooled to below 0°C. 7.0 g (8.0 mol/L) of sodium nitrite aqueous solution was slowly added dropwise thereto, and the mixture was stirred at 5° C. or lower for 1 hour to obtain a diazotized solution.

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

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

(Production Example 4): Production of Pigment Derivative 4 In 630 g of concentrated sulfuric acid (98%), 35.0 g (121 mmol) of DPP pigment (manufactured by BASF, Irgazin Scaret L 3550 HD, C.I. Pigment Red 255) was added. Paraformaldehyde: 4.50 g and 4-aminophthalimide: 24.7 g were added and reacted at 30° C. for 5 hours. Next, this reaction solution was discharged into 3 L of cold water, filtered and washed with water to obtain a water paste of 400 g (solid content) of a 4-aminophthalimidomethyl DPP pigment derivative into which one 4-aminophthalimidomethyl group was introduced. :11.2%).

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

(Production Example 5): Production of Pigment Derivative 5 Instead of Irgazin Scaret L 3550 HD, manufactured by BASF, T-99 CRUDE BLUE (phthalocyanine pigment, C.I. Pigment Blue 15, manufactured by Zhuhai Toyo Shikizai Co., Ltd.) was used. ) was used, but in the same manner as in Production Example 1, 74.3 g of Pigment Derivative 5 was obtained. In the same manner as in Production Example 1, it was confirmed that the peak of the target product (m/z=840) was present in the negative mode spectrum using DHBA as the matrix. That is, it was confirmed that pigment derivative 5 contains a compound represented by formula (1) (dye residue Q is a residue of a phthalocyanine pigment, and X is a methylene group).

(Production Example 6): Production of Pigment Derivative 6 22.2 g (50.0 mmol) of Cinilex Red SR3C (anthraquinone pigment, C.I. Pigment Red 177) manufactured by Cinic was added to 175 g of 78% sulfuric acid. did. After cooling to 0° C. or lower, 23.3 g (8.0 mol/L) of sodium nitrite aqueous solution was slowly added dropwise and stirred at 5° C. or lower for 1 hour to obtain a diazotized liquid. 28.0 g of 30% aqueous sodium hydroxide solution and 28.6 g of 3PY were added and dissolved in 360 g of ion-exchanged water. Furthermore, 600 g of 50% aqueous sodium acetate solution was added, and the liquid temperature was adjusted to 20°C. The diazotized solution was added dropwise from the dropping funnel to this. The pH after dropping was 4.4. After stirring at 20°C for 1 hour, the temperature was raised to 60°C, and further stirred at this temperature for 1 hour. After the reaction, the reaction solution was cooled to 50° C., adjusted to pH<2 with 35% hydrochloric acid, and filtered under suction. The filtrate was washed with 3 L of ion-exchanged water and dried at 80° C. to obtain 48.1 g of pigment derivative 6.

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

(Production Example 7): Production of Pigment Derivative 7 Except for using Cinilex Red SR3C (anthraquinone pigment, C.I. Pigment Red 177), manufactured by Cinic, in place of Irgazin Scaret L 3550 HD, manufactured by BASF, In the same manner as in Production Example 4, 42.8 g of pigment derivative 7 having the structure of formula (3) below was obtained. In the same manner as in Production Example 1, it was confirmed that the peak of the target product (m/z=884) was present in the negative mode spectrum using DHBA as the matrix.

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

The components listed in Table 1 used in the following Examples and Comparative Examples are as follows. The components listed in Table 1 are shown in parentheses.

<Pigment>
1)C. I. Pigment Blue 15:6 (PB15:6)
FASTOGEN Blue EP-207, manufactured by DIC Corporation 2) C. I. Pigment Red 254 (PR254)
Iragzin (registered trademark) Red L3630, manufactured by BASF 3) C. I. Pigment Yellow 139 (PY139)
Iragzin (registered trademark) Yellow S2150CF, manufactured by BASF 4) C. I. Pigment Red 209 (PR209)
Fastogen Super RED 209 228-6736, manufactured by DIC Corporation

<Dispersant>
1) Disperbyk LPN6919 (LPN6919), manufactured by BYK Chemie Japan Co., Ltd. 2) Disperbyk LPN21116 (LPN21116), manufactured by BYK Chemie Japan Co., Ltd.

<Dispersion resin>
SPC-2000 (SPC2000), manufactured by Showa Denko K.K.

<Pigment derivative>
Solsperse 12000 (Solsperse), manufactured by Japan Lubrizol Co., Ltd.

<Solvent>
Propylene glycol monomethyl ether acetate (PMA), manufactured by Kyowa Hakko 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 charged into a sand mill so as to have the composition shown in Table 1. After stirring at 2000 rpm for 10 minutes, 800 g of zirconia beads with a diameter of 0.5 mm were added, and a dispersion treatment was performed at 2000 rpm for 2 hours. Thereafter, the zirconia beads were removed to obtain pigment dispersions 1 to 10. In Comparative Example 4, Pigment Red 209, which is the raw pigment of Production Example 8, was used instead of the pigment derivative. Moreover, the unit of the component composition in Table 1 is weight %.

<Preparation of colored composition for coating film formation>
Alkali-soluble resin (manufactured by Nippon Shokubai Co., Ltd., Acrycure (registered trademark) BX-Y-10, acrylic polymer): 12.0% by weight, polyfunctional acrylate monomer (dipentaerythritol) as a photopolymerizable component Hexa/penta)acrylate, manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA): 26.0% by weight, photopolymerization initiator (manufactured by BASF Japan, Irgacure 369): 4.0% by weight, PMA as a solvent: 58.0% by weight A coating film-forming component containing the following was prepared.

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

<Evaluation>
<<<Viscosity of pigment dispersion>>
The viscosity of the obtained pigment dispersions 1 to 10 immediately after preparation was measured using an E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd. The measurement results are shown in Table 1.

<<Contrast of paint film>>
In the case of the colored composition for forming a blue paint film prepared in Example 4 and Comparative Example 2, the chromaticity is y = 0.107, and for the coloring composition for forming a red paint film prepared in other Examples and Comparative Examples. In the case of a colored composition, using a spin coater (manufactured by Mikasa Co., Ltd., spin coater MS-150A) adjusted to a rotation speed such that the chromaticity x = 0.648, the above-mentioned coating was applied to a 1 mm thick, 100 mm square glass plate. The colored composition for forming a coating film obtained as above was applied. This coated plate was allowed to stand at room temperature for 5 minutes, and then dried (prebaked) in an air bath at 80° C. for 2 minutes. Furthermore, using an exposure device (manufactured by Sanei Denki Seisakusho Co., Ltd., product name: UVE-1001S type exposure light source device, YSH-100SA type ultra-high pressure mercury lamp), ultraviolet rays (UV) were emitted to an exposure intensity of 60 mJ/ ^cm2 . was applied to the coated plate, and post-baking was performed at 235°C for 30 minutes. The coated plate after post-baking was placed on top of a lamp (trade name: HF-LS-100WLCG), sandwiched between polarizing plates (trade name: POLAX-38S, manufactured by Luceo Co., Ltd.). The brightness when the polarizing plates are in the crossed nicol position and the brightness when the polarizing plates are in the parallel position were measured using a colorimeter (product name: LS-100, manufactured by Konica Minolta Sensing Co., Ltd.). , the ratio (%) was calculated as contrast (CR). The values are shown as a ratio to Comparative Example 1 for Examples 1 to 3, and to Comparative Examples 2 to 4 for Examples 4 to 6, respectively. The results are shown in Table 1.

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, and Example 6 and Comparative Example 4, specific pigment derivatives were It can be seen that by using the pigment dispersion, the dispersibility of the pigment dispersion is good and the contrast of the coating film is improved.

Claims (3)

Containing at least one pigment derivative selected from the compounds represented by the following formula (1), a pigment, a dispersant and a solvent,
A pigment dispersion, wherein Q in formula (1) is a residue of a pigment selected from phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, and quinacridone pigments.

(In formula (1), Q represents a dye residue, and 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 ** indicate bonds.) A coloring composition for forming a paint film, comprising the pigment dispersion according to claim 1 and a paint film-forming component. The coloring composition for forming a paint film according to claim 2, which contains a photopolymerizable component as the paint film forming component.