JP2018172619A - Coumarin compound or salt thereof, and pigment composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition stable as a colorant of e.g., a resist for color filters, where a pigment composition containing an organic pigment is reduced in particle size and increased in concentration without causing aggregation, sedimentation, or a viscosity increase with time.SOLUTION: The present invention provides a coumarin compound represented by a formula (1) or a salt thereof and a composition thereof (where, R-Rare H, a C1-4 alkyl group, a C1-4 alkoxy group, an amino group, a C1-4 alkylamino group, a C1-4a dialkylamino group, a halogen atom, a -COM group or a -SOM group; M is H, an alkali metal atom, an alkaline earth metal atom or a -NZZZZgroup; Z-Zindependently represent H or a C1-4 alkyl group or the like).SELECTED DRAWING: None

Description

  The present invention relates to resists for color filters used in the production of liquid crystal displays and imaging devices, coumarin compounds used in ink jet inks or salts thereof, and pigment compositions excellent in fluidity and transparency containing the compounds. About.

  In recent years, pigments have been used as colorants for paints and printing inks, and in recent years for color filter resists and inkjet inks. Pigments have various characteristics such as heat resistance, weather resistance, migration resistance, etc., and are excellent in fastness compared to dyes, but on the other hand, aggregation, sedimentation, increase in viscosity over time, dissimilarity It has potential problems such as color separation when mixed with pigments.

  Recently, in order to achieve high contrast in liquid crystal displays, miniaturization of image sensors, high coloring and high definition of ink-jet inks, etc., there has been a demand for finer pigments and higher pigment concentrations in pigment compositions. However, as the particle diameter becomes finer and the pigment concentration increases, aggregation tends to occur and it is difficult to obtain a stable dispersion.

  In order to solve these problems, improvement of the pigment itself (pigment surface treatment), the development of a dispersant having a good adsorptivity to the pigment, the development of a surfactant, and the proposal of pigment derivatives have been made so far. I came. A pigment derivative is a compound in which substituents such as acidity and basicity are introduced into a pigment having the same structure or a similar structure as that of a finely divided pigment, and has an affinity and adsorbability with the pigment and has an acid-base interaction. Therefore, it has a property of improving the fine particle formation and dispersion stability of the pigment, and is used in the process of pulverizing and dispersing fine particles of the pigment. As pigments used in color filters and inkjets, phthalocyanine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, isoindoline pigments, isoindolinone pigments, azo pigments, There are dye lake pigments, and many pigment derivatives have been reported, particularly phthalocyanine pigments, anthraquinone pigments, and quinacridone pigments. For example, a method of mixing a sulfonated pigment or a metal salt thereof with a pigment (Patent Documents 1 to 3), a method of mixing a substituted aminomethyl derivative (Patent Document 4), a method of mixing a phthalimidomethyl derivative (Patent Document 5), etc. It has been known.

Although these methods are effective for pigments having a specific skeleton, the number of substituents to be introduced can be reduced for pigments that are structurally difficult to introduce sulfone groups, aminomethyl groups, phthalimidomethyl groups, etc. It is difficult to control the position, and as a result, the effect as a dispersant is insufficient, and a by-product that adversely affects the color tone is produced in a large amount, and the quality of the pigment dispersion is not stable.
In addition, the pigment composition using Pigment Red 254, which has been widely used as a red pigment for color filters, has had a problem of improving the transmittance.

Japanese Patent Publication No.41-2466 JP 63-172772 A Japanese Patent Publication No. 50-4019 Japanese Examined Patent Publication No. 39-16787 JP-A-55-108466 U.S. Pat. No. 4,749,795

  The problem to be solved by the present invention is C.I. I. Pigment Red 254 and other pigments containing organic pigments such as red pigments (pigment dispersions) are made finer and highly concentrated without causing aggregation, sedimentation, and increase in viscosity over time. It is to provide a stable composition (dispersion) as a color filter resist or a colorant for inkjet ink.

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a compound comprising a coumarin derivative, and has completed the present invention.
That is, the present invention
(1) The following formula (1)

(In the formula (1), R _{1 to} R ₇ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, an alkylamino group having 1 to 4 carbon atoms, and 1 carbon atom. To 4 dialkylamino groups, halogen atoms, —CO ₂ M groups or —SO ₃ M groups, where M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or —NZ ₁ Z ₂ Z ₃ Z ₄ group; Z _{1 to} Z ₄ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an aralkyl group, a cycloalkyl group having 5 or 6 carbon atoms, or an aryl group. Or a C 1 -C 4 alkyl group substituted by a C 5 or C 6 cycloalkyl group.) Or a salt thereof,
(2) At least one of R _{1 to} R ₇ is a —CO ₂ M group or —SO ₃ M group, and M is a hydrogen atom, sodium atom, potassium atom, cesium atom, calcium atom, barium atom or rosin ammonium ( A coumarin compound or a salt thereof according to item (1), which is Abieta-8,11,13-triene-18-ammonium),
(3) The coumarin compound or a salt thereof according to item (2), wherein R _{1 to} R ₇ are a hydrogen atom or a —SO ₃ M group,
(4) A pigment composition comprising the coumarin compound according to any one of (1) to (3) or a salt thereof, an organic pigment and a resin dispersant,
(5) The pigment composition according to (4), wherein the resin dispersant is a cationic resin dispersant;
(6) The pigment composition as described in (4) or (5) above, wherein the addition amount of the coumarin compound or a salt thereof is 1 to 50 parts by mass with respect to 100 parts by mass of the organic pigment.
(7) The pigment composition according to any one of (4) to (6), wherein the organic pigment is a pigment having a diketopyrrolopyrrole skeleton,
(8) A color resist containing the pigment composition according to any one of (4) to (7), a binder resin, and a polymerizable compound,
(9) The inkjet ink composition containing the coumarin compound or the salt thereof according to any one of (1) to (3), and (10), further comprising at least one organic solvent. (9) The ink composition for inkjet according to
About.

  The coumarin compound represented by the formula (1) of the present invention or a salt thereof is very easy to produce, and by using this compound, C.I. I. Pigment Red 254 and other pigment compositions containing pigments can be made finer and highly concentrated without causing aggregation, sedimentation, and increase in viscosity over time. Colorants for color filter resists and inkjet inks As a result, a stable dispersion can be obtained.

The present invention is described in detail below.
The coumarin compounds or their salts of the present invention have a structure represented by the following formula (1).

  The coumarin compound of the present invention or a salt thereof can be suitably used as a color filter resist or a colorant for inkjet ink. Hereinafter, for convenience, the “coumarin compound of the present invention or a salt thereof” may be simply described as “the compound of the present invention”.

In the formula (1), R _{1 to} R ₇ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, an alkylamino group having 1 to 4 carbon atoms, and 1 to 4 represents a dialkylamino group, a halogen atom, a —CO ₂ M group or a —SO ₃ M group. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a —NZ ₁ Z ₂ Z ₃ Z ₄ group. Z _{1 to} Z ₄ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an aralkyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group, or 5 carbon atoms. Alternatively, it represents an alkyl group having 1 to 4 carbon atoms substituted by a cycloalkyl group having 6 carbon atoms.
The alkyl group having 1 to 4 carbon atoms represented by R _{1 to} R _{7 in} the formula (1) may be either linear or branched, but is preferably linear, and specific examples thereof include a methyl group, Examples include an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and a methyl group or an ethyl group is preferable.
The alkoxy group having 1 to 4 carbon atoms represented by R _{1 to} R _{7 in} the formula (1) may be either linear or branched, but is preferably linear, and specific examples thereof include a methoxy group, An ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and the like can be mentioned, and a methoxy group or an ethoxy group is preferable.

The alkyl group of the alkylamino group having 1 to 4 carbon atoms represented by R _{1 to} R _{7 in} the formula (1) may be either linear or branched, but is preferably linear. Specific examples of the alkylamino group having 1 to 4 carbon atoms include methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, sec-butylamino group and tert-butyl. An amino group etc. are mentioned, Preferably they are a methylamino group or an ethylamino group.
The alkyl group contained in the dialkylamino group having 1 to 4 carbon atoms represented by R _{1 to} R _{7 in} the formula (1) may be either linear or branched, but is preferably linear. Specific examples of the dialkylamino group having 1 to 4 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-sec- Examples thereof include a butylamino group and a di-tert-butylamino group, and a dimethylamino group or a diethylamino group is preferable.
Specific examples of the halogen atom represented by R _{1 to} R _{7 in} the formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a bromine atom or a chlorine atom.

Specific examples of the alkali metal atom and alkaline earth metal atom represented by M in the formula (1) include lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, francium atom, calcium atom, strontium atom, barium atom. And a radium atom, preferably a lithium atom, a sodium atom, a potassium atom, a cesium atom, a calcium atom, a strontium atom or a barium atom, more preferably a cesium atom, a calcium atom or a barium atom, It is more preferably an atom or a calcium atom, and particularly preferably a cesium atom.
In addition, when at least one of R _{1 to} R ₇ represents a —CO ₂ M group or —SO ₃ M group and M is an alkaline earth metal, the —CO ₂ M group or the —SO ₃ M group One positive charge that does not participate in the binding may be bonded to any substance or compound having a negative charge, and these are all coumarin compounds having the structure represented by the formula (1) of the present invention or Included in the category of those salts.

Specific examples of the alkyl group having 1 to 4 carbon atoms represented by Z _{1 to} Z ₄ in formula (1) include specific examples of the alkyl group having 1 to 4 carbon atoms represented by R _{1 to} R ₇ in formula (1). The same thing is mentioned, and a preferable thing is also the same.
Specific examples of the hydroxyalkyl group represented by Z _{1 to} Z ₄ in the formula (1) include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, 3- A hydroxybutyl group, 2-hydroxybutyl group, etc. are mentioned, Preferably it is a hydroxyethyl group.
Specific examples of the aralkyl group represented by Z _{1 to} Z ₄ in the formula (1) include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group, and a benzyl group is preferable.
Specific examples of the cycloalkyl group having 5 or 6 carbon atoms represented by Z _{1 to} Z _{4 in} formula (1) include a cyclopentyl group and a cyclohexyl group, and a cyclohexyl group is preferable. The cycloalkyl group mentioned here may be increased with a saturated hydrocarbon ring and / or an unsaturated hydrocarbon ring, and the hydrogen atom on the ring of the cycloalkyl group and / or the hydrogen atom on the increase is an alkyl group. It may be substituted with a substituent such as a group. Specific examples of the —NZ ₁ Z ₂ Z ₃ Z ₄ group having a ring-increased and having an alkyl group and a cycloalkyl group having 5 or 6 carbon atoms include rosin ammonium (Abieta-8, 11, 13). -Triene-18-ammonium) is preferred.
Specific examples of the aryl group represented by Z _{1 to} Z ₄ in the formula (1) include a phenyl group and a naphthyl group, and a phenyl group is preferable.

The alkyl group having 1 to 4 carbon atoms substituted by the cycloalkyl group having 5 or 6 carbon atoms represented by Z _{1 to} Z _{4 in} formula (1) is a cycloalkyl group having 5 or 6 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms, ie, a cycloalkyl-substituted alkyl group, as the substituent, ie, a cycloalkyl group having 5 or 6 carbon atoms in the cycloalkylalkyl group include those represented by the formula (1) Specific examples of the cycloalkyl group having 5 or 6 carbon atoms represented by Z _{1 to} Z ₄ therein can be given, and specific examples of the alkyl group having 1 to 4 carbon atoms in the cycloalkyl group include Specific examples of the alkyl group having 1 to 4 carbon atoms represented by R _{1 to} R ₇ in formula (1) are the same.

  M in the formula (1) is preferably a hydrogen atom, a barium atom, a calcium atom, a cesium atom or rosin ammonium (Abieta-8,11,13-triene-18-ammonium), and a cesium atom or rosin ammonium (Abieta-8, 11,13-triene-18-ammonium) is more preferred.

The coumarin compounds represented by the formula (1) of the present invention or salts thereof include R _{1 to} R ₇ (and —CO ₂ M group, —SO ₃ M group and —NZ ₁ Z ₂ Z ₃ Z _4). In the group, M, Z _{1 to} Z ₄ ) are preferably a compound in which the respective preferable ones are combined or a salt thereof, more preferably a compound in which the more preferable ones are combined or a salt thereof.

  Examples of the amine used when salting the compound of the formula (1) include ammonia, diethylamine, triethanolamine, benzylamine, rosinamine (18-aminoabieta-8,11,13-triene) and the like.

  The salt of the coumarin compound represented by the formula (1) may be a free acid, a tautomer thereof, or a mixture of these various salts. For example, any combination such as a mixture of cesium salt and ammonium salt, a mixture of free acid cesium salt, a mixture of lithium salt, calcium salt and cesium salt may be used. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, select the type of salt as appropriate, or change the ratio when containing multiple salts, etc. It is also possible to obtain a mixture having

The coumarin compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method.
That is, a desired compound can be obtained by subjecting a compound represented by the following formula (2) and a compound represented by the following formula (3) to a condensation reaction. In the following formulas (2) and (3), R _{1 to} R ₇ represent the same meaning as in the above formula (1), and R ₈ represents a hydrogen atom, a methyl group or an ethyl group.

  Specific examples of the compound of the present invention are shown below. In addition, the acidic functional group of a compound shall be represented in the form of a free acid for convenience.

The pigment composition of the present invention contains the compound of the present invention, an organic pigment and a resin dispersant.
The organic pigment contained in the pigment composition of the present invention is not particularly limited as long as it is a conventionally known one such as those described in the color index, but the compound represented by the formula (1) of the present invention itself is a red type. Since it has a hue, it is preferable to use a red organic pigment in the sense that it does not impair the original hue of the organic pigment, more preferably an organic pigment classified as pigment red by color index. I. Pigment Red 254 is more preferable. In addition, the organic pigment contained in the pigment composition is preferably an organic pigment having a diketopyrrolopyrrole skeleton in the sense that it is excellent in dispersion stability when mixed with the compound of the present invention.

  The resin dispersant contained in the pigment composition of the present invention is not particularly limited as long as it is a known resin dispersant, but a cationic resin dispersant is preferable in view of affinity with the compound of the present invention. Examples of cationic resin dispersants include BYK112, 116, 140, 142, 161, 162, 164, 166, 182, 2000, 2001, 2050, 2070, 2150 from Big Chemie Japan, EFKA4010 from Efka Corporation, 4015, 4020, 4050, 4055, 4060, 4300, 4330, 4400, 4406, Solsperse of Nippon Lubrizol Corporation, 24000, 32500, Ajimoto Fine Techno Co., Ltd. Ajisper PB711, 821, 822, 881 and the like. The addition amount of the resin dispersant is usually 5 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the organic pigment. When the addition amount of the resin dispersant is less than 5 parts by mass, good dispersion stability cannot be obtained.

  If necessary, an organic solvent can be added to the pigment composition of the present invention. The organic solvent that can be used is not particularly limited, for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve, cyclohexanone, cyclopentanone, ethylene glycol diethyl ether, Examples include diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, methanol, ethanol, and isopropyl alcohol. These may be used alone or in admixture of two or more. The organic solvent is used in an amount of 90% by mass or less in the pigment composition.

The color resist of the present invention contains the pigment composition of the present invention, a binder resin and a polymerizable compound.
The binder resin that can be used in the color resist of the present invention is not particularly limited. For example, styrene (co) polymer, (meth) acrylic acid ester (co) polymer, styrene-maleic acid ester copolymer, cellulose Examples thereof include acetate-based resins, polyester-based resins, polyurethane-based resins, polyamide-based resins, and polyimide-based resins. These may be used alone or in combination of two or more. The binder resin is used in an amount occupying 50% by mass or less in the pigment composition.

Examples of the polymerizable compound that can be used in the color filter resist of the present invention include a photopolymerizable monomer, an epoxy compound, and a melamine compound. Specific examples of these polymerizable compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth). Acrylate, triethyleneglycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, bisphenol-A type epoxy di (meth) acrylate, bisphenol Nord-F type epoxy di (meth) acrylate, bisphenol-fluorene type epoxy di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate , Ethoxylated isocyanuric acid tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, cayarad RP-1040 (Nippon Kayaku), Kayrad DPCA-30 (Nippon Kayaku), UA-33H (Shin Nakamura Chemical), UA-53H (Shin Nakamura Chemical) and M-8060 (Toagosei) (Meth) acrylate monomers: TEMPIC (manufactured by Sakai Chemical), TMMP (manufactured by Sakai Chemical), thiol polymerization monomers such as PMP (manufactured by Sakai Chemical) and DPMP (manufactured by Sakai Chemical); NC-6000 of Nippon Kayaku products NC-6300, NC-6300H, NC-3000, EOCN-1020, XD-1000, EPPN-501H, BREN-S, NC-7300L, Daicel Chemicals' Celoxite 2021P, EHPE3150, Cyclomer M100, Epolide PB3600, Japan Epoxy Resin products Epicoat 828, Epicoat YX8000, Epicoat YX4000, Printec products VG-3101L, Silaace S510 (Nisso), TEPIC (Nissan Chemical Industries) and other epoxy compounds; and methylolated melamine and Mw Melamine-based compounds such as -30 (Sanwa Chemical) are mentioned, but are not limited thereto.
These polymerizable compounds are preferably used in combination with a polymerization initiator, a curing accelerator or the like, if necessary.

  Other additives that can be added to the pigment composition of the present invention as necessary include, for example, thixotropic agents, polymerization initiators and curing agents, curing accelerators, polymerization inhibitors, organic or inorganic fillers, coupling agents, and the like. Although these may be mentioned, these may be selected according to the specific intended use of the pigment composition, and are not limited to the above. Further, the addition amount may be selected in accordance with a specific purpose application.

  The pigment composition of the present invention can be prepared, for example, by the following method. That is, as a method of blending the organic pigment and the compound of the present invention, various conventionally known methods, for example, a method of simply mixing each dry powder or press cake, various dispersions such as a kneader, a bead mill, a dissolver, an attritor, etc. Examples thereof include a method of mechanically mixing by a machine, a method of suspending an organic pigment in water or an organic solvent, and adding and mixing the compound of the present invention therein to deposit uniformly on the surface of the organic pigment. Next, a mixture of the obtained organic pigment and the compound of the present invention is blended with a resin dispersant and various organic solvents, a binder resin, various additives, etc. as necessary, and a sand mill, an annular bead mill, an attritor, etc. The desired pigment composition can be produced by dispersing in step (b). Alternatively, for convenience, the organic pigment, the compound of the present invention, the resin dispersant, and other components as necessary may be mixed and dispersed in a lump. The addition amount of the compound of the present invention in the pigment composition of the present invention is usually 0.1 to 70 parts by weight, preferably 0.5 to 60 parts by weight, more preferably 100 parts by weight of the organic pigment. 1 to 50 parts by mass. If the compounding ratio of the compound of the present invention is too small, the desired dispersion stability and fine particle formation of the organic pigment cannot be achieved, and even if the compounding ratio is excessively increased, the dispersion stability is decreased. Optimization is necessary.

  The use of the pigment composition of the present invention is not particularly limited. For example, various printing inks such as gravure printing inks, paints, dry toners or wet toners for electrophotography, inks for inkjet recording, resist colorants for color filters, and the like. Applications are listed. In particular, the pigment composition of the present invention is useful as a resist colorant for color filters and ink for ink jet recording that require finer pigments and high stability.

  Hereinafter, the present invention will be described specifically by way of examples. In the text, “parts” and “%” are based on mass unless otherwise specified. The maximum absorption wavelength in the examples is a value measured by a spectrophotometer “UV-3150 manufactured by Shimadzu Corporation”, and the acid value is a value measured by a measurement method based on JIS K-0070: 1992. The weight average molecular weight is a value calculated in terms of polystyrene based on the measurement result of gel permeation chromatography.

Example 1 (Synthesis of the compound represented by No. 1 of the above specific example compound)
(Process 1)
9 parts of ethyl coumarin-3-carboxylate, 6.8 parts of 5,6-diaminobenzimidazolone and 76 parts of 85% phosphoric acid were added to the reaction vessel, reacted at 150 ° C. for 1 hour, then cooled to 80 ° C. The reaction solution was added to 400 parts of ice to obtain “Suspension 1”. After filtering “Suspension 1”, 50 parts of the obtained “Wet Cake 1” was dried with a hot air dryer at 80 ° C. to obtain 14 parts of a compound represented by the following formula (4).

(Process 2)
70 parts of 30% fuming sulfuric acid was added to 70 parts of sulfuric acid at 10 ° C. or less, 10 parts of the compound represented by the formula (4) obtained in Step 1 was slowly added at 5 to 10 ° C., and then 3 hours at room temperature. The mixture was stirred, then heated to 40 ° C. and further reacted for 1 hour. After cooling to room temperature, this reaction solution was dropped into 800 parts of ice in about 10 minutes, and then the pH value was adjusted to 8 to 9 with a 25% aqueous sodium hydroxide solution to obtain 1.8 L of “aqueous solution 1”. .

(Process 3)
An aqueous solution prepared by dissolving 1.9 parts of 18-aminoabieta-8,11,13-triene in 18 parts of 3.3% acetic acid aqueous solution was added to 0.6 L of “Aqueous solution 1” obtained in step 2, and 50 ° C. For 1 hour. The “wet cake 2” obtained by filtering the reaction solution was dried with a hot air dryer at 80 ° C. 4.6 parts of the compound represented by 1 were obtained. The maximum absorption wavelength λmax of the compound was 422 nm (NMP).

Example 2 (Synthesis of a compound represented by No. 2 of the above specific example compound)
(Process 4)
3. Instead of using an aqueous solution in which 1.9 parts of 18-aminoabieta-8,11,13-triene was dissolved in 18 parts of a 3% aqueous acetic acid solution, 8.8 parts of cesium chloride were used, and Except having changed the usage-amount from 0.6L to 1.2L, it carried out similarly to the process 3, and carried out specific example compound No.2. 7 parts of the compound represented by 2 were obtained. The maximum absorption wavelength λmax of the compound was 422 nm (NMP).

Synthesis example 1 (adjustment of binder resin A)
A 500 ml four-necked flask is charged with 160 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 33 parts of benzyl methacrylate, and 1 part of α, α'-azobis (isobutyronitrile), and nitrogen gas is introduced into the flask for 30 minutes while stirring. did. Then, it heated up to 80 degreeC and stirred for 4 hours as it was at 80 to 85 degreeC. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a colorless, transparent and uniform binder resin solution. This was precipitated in a 1: 1 mixed solution of isopropyl alcohol and water, filtered, and the solid content was taken out and dried to obtain a binder resin A. The obtained binder resin A had a polystyrene equivalent weight average molecular weight of 18,000 and an acid value of 152.

Example 3 (Preparation of the pigment composition of the present invention)
As an organic pigment, C.I. I. Pigment Red 254 10.0 parts, No. obtained in Example 1 as a compound of the present invention. 1.0 parts of the compound represented by 1; 1.8 parts of the binder resin A obtained in Synthesis Example 1 as the binder resin; Azisper PB881 (manufactured by Ajinomoto Fine Techno Co.) as the resin dispersant; 82 parts of propylene glycol monomethyl ether acetate as the solvent After premixing, the mixture was dispersed with a paint shaker for 60 minutes using 0.3 mm zirconia beads. The obtained dispersion was filtered through a 5 μm filter to prepare a pigment composition.

Example 4 (Preparation of the pigment composition of the present invention)
No. 1 obtained in Example 1. No. 1 obtained in Example 2 instead of the compound represented by No. 1. A pigment composition was prepared in the same manner as in Example 3 except that the compound represented by 2 was used.

Comparative Example 1 (Preparation of comparative pigment composition)
No. 1 obtained in Example 1. A pigment composition was prepared in the same manner as in Example 3 except that the compound represented by 1 was not used.

The pigment compositions of Examples 3 and 4 and Comparative Example 1 were measured for viscosity using a B-type viscometer at room temperature (25 ° C.) of 10 rpm and evaluated according to the following criteria. In order to confirm the storage stability, in addition to the initial (immediately after adjustment), the viscosity after standing at 40 ° C. for 3 days was also measured and evaluated. The results are shown in Table 1.
Evaluation criteria Initial viscosity: less than 20 mPa · s ○, 20 mPa · s or more ×
40 ° C. × 3 days later viscosity increase rate: less than 20% ○, 20% or more ×
In addition, about the thing gelatinized immediately after preparation, the viscosity after leaving to stand at 40 degreeC for 3 days was set to "it cannot evaluate."

As is apparent from Table 1, the pigment compositions of Examples 3 and 4 have a lower initial viscosity than that of Comparative Example 1 in which the present pigment derivative is not added. And the quality of the ink is not impaired. Furthermore, the storage stability was better than that of the comparative example.
Specifically, Comparative Example 1 was not dispersible due to gelation, whereas Examples 3 and 4 had a viscosity increase rate of 20% or less after 40 ° C. × 3 days.

By using the coumarin compound of the present invention, it is possible to make fine particles and increase the concentration without increasing aggregation, sedimentation, and viscosity over time, and pigment derivatives are used in color filter resists and inkjet inks. As a colorant, it is very useful for obtaining a stable dispersion.

Claims (10)

Following formula (1)

(In the formula (1), R _{1 to} R ₇ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an amino group, an alkylamino group having 1 to 4 carbon atoms, and 1 carbon atom. To 4 dialkylamino groups, halogen atoms, —CO ₂ M groups or —SO ₃ M groups, where M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or —NZ ₁ Z ₂ Z ₃ Z ₄ group; Z _{1 to} Z ₄ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an aralkyl group, a cycloalkyl group having 5 or 6 carbon atoms, or an aryl group. Or a C 1 -C 4 alkyl group substituted by a C 5 or C 6 cycloalkyl group.) Or a salt thereof. At least one of R _{1 to} R ₇ is a —CO ₂ M group or —SO ₃ M group, and M is a hydrogen atom, sodium atom, potassium atom, cesium atom, calcium atom, barium atom or rosin ammonium (Abieta-8 , 11,13-triene-18-ammonium), or a coumarin compound or a salt thereof. The coumarin compound or a salt thereof according to claim 2, wherein R _{1 to} R ₇ are a hydrogen atom or a —SO ₃ M group. A pigment composition comprising the coumarin compound according to any one of claims 1 to 3 or a salt thereof, an organic pigment, and a resin dispersant. The pigment composition according to claim 4, wherein the resin dispersant is a cationic resin dispersant. The pigment composition according to claim 4 or 5, wherein the addition amount of the coumarin compound or a salt thereof is 1 to 50 parts by mass with respect to 100 parts by mass of the organic pigment. The pigment composition according to any one of claims 4 to 6, wherein the organic pigment is a pigment having a diketopyrrolopyrrole skeleton. A color resist comprising the pigment composition according to claim 4, a binder resin, and a polymerizable compound. An ink-jet ink composition comprising the coumarin compound according to any one of claims 1 to 3 or a salt thereof. Furthermore, the ink composition for inkjets of Claim 9 containing at least 1 or more types of organic solvent.