WO2011030810A1 - Dye derivative, colorant, and coloring method - Google Patents

Abstract

Disclosed is a pigment derivative, characterized by being a dye derivative obtained by linking the molecule of a water-insoluble dye (A) and the residue of a compound (C) to each other through an alkylene group formed by reacting the dye (A) with an aldehyde compound (B). By appropriately selecting the compound (C) from hydrocarbon compounds (C-1) having a methane group (-CH=) with a hydrogen group which is susceptible to substitution and amino compounds (C-2) having a reactive amino group, a deeper color effect than the color of an existing dye is brought about. Further, by using a pigment derivative effective as an additive for suppressing the crystal transfer or crystal growth of a pigment and also using the dye derivative, a colorant which has the above-mentioned effect, and also achieves a decrease in the viscosity of a pigment dispersion and has improved properties such as dispersion stability and long-term storage stability is realized. By using this colorant, a useful coloring method and a colored article are provided.

Description

Dye derivative, coloring agent and coloring method

The present invention relates to a pigment derivative, a colorant, and a coloring method. More specifically, a dye derivative in which a compound having a methine group or an amino group is linked to the molecular structure of a water-insoluble dye via an alkylene group, a colorant containing the same, a coloring method for an article using the same, and a colored article It is about.

Conventionally, as dyes used for coloring articles, dyes that are soluble in water and solvents, and pigments that are insoluble in those media and finely dispersed in fine particles are usually used. However, dyes have many simple pigments as molecular structures, and the color has excellent transparency and sharpness, but has a problem in fastness such as light resistance and heat resistance. In addition, pigments have a lower color tone and sharpness than dyes, and many have crystal forms, some of which are unstable to organic solvents and heat, and crystal transitions and particles become coarse, resulting in color changes. Sometimes changed. Liquid pigments of pigments are often dispersed in liquid media such as solvents and water and tend to settle or aggregate, and even if improved with a dispersion aid, they will aggregate for a long time. It had drawbacks, such as a problem in sex.

With regard to the color tone of dyes, for example, expression in a wider color gamut has been demanded as a color printing expression for information recording in laser printers and color copiers, and a colorant that can cope with this has been demanded. ing. In particular, there is a demand for a greener blue pigment than β-type copper phthalocyanine (CI Pigment Blue 15: 3), which is a blue pigment used in cyan toner. Moreover, as a greenish blue oil-soluble dye, there is a dye (for example, CI Solvent Blue 25) in which an alkyl group is introduced with a sulfoamide group as a linking group in the molecular structure of copper phthalocyanine. Although effective in terms of functionality such as control and redispersibility, when the amount is increased as a green component of the color toner, there is a problem in light resistance of the printed matter.

In addition, reddish blue ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) is used as a blue pigment used for forming a blue pixel of an image display material of a color filter. Slightly unstable to heat. For this reason, monosulfonated copper phthalocyanine is often used as an additive for suppressing pigment crystal transition and crystal growth, but it tends to have a green hue and lower saturation. It is not preferable in terms of color tone for blue pixels of taste blue. That is, there is a demand for a pigment derivative that can achieve a better color tone without impairing the color tone of the original pigment.

Japanese Patent No. 3685863

Conventionally used direct dyes and acid dyes are synthesized for the purpose of dyeing woven fabrics such as cotton and nylon, and have sufficient fastness required for pigments including the current information field. There is a demand for pigments that are not satisfactory and have excellent fastness properties such as light resistance. Further, in terms of color, in the field of information recording such as digital printing, dyes that can achieve a wide color gamut that cannot be obtained by conventional dyes, in particular, sky blue dyes are expected. Also, development of pigment derivatives effective as additives for suppressing pigment crystal transition and crystal growth, improvement of dispersibility of organic solvent-based dispersed color pigments, reduction of dispersion viscosity, and dispersion stability There is a demand for the development of a dispersion aid that improves the storage stability and other performance.

Therefore, an object of the present invention is to develop a pigment derivative based on an existing pigment skeleton in order to improve the fastness and color tone of these pigments economically and efficiently.

As a result of intensive studies to achieve the above object of the present invention, the present inventors have found the following to arrive at the present invention when synthesizing a pigment derivative. That is, by reacting a compound (B) for forming an alkylene group with the water-insoluble dye (A) and a compound (C) having a reactive methine group or amino group, a dye molecule such as a pigment and the alkylene A new dye derivative in which a group is bonded by a carbon-carbon bond and the residue of the compound (C) is linked to the other end of the alkylene group is obtained, and by using these, the above-mentioned problems can be solved. I found.

That is, the present invention is a derivative of a water-insoluble dye used as a colorant, which is a water-insoluble dye (A) and an aldehyde compound (B) that can react with the water-insoluble dye (A) to form an alkylene group. And a hydrocarbon compound having a methine group (—CH═) having an easily replaceable hydrogen group and its derivative (C-1), an amino compound having a reactive amino group and a derivative (C-2) thereof A derivative of a dye obtained by reacting any one of the compounds (C) selected from the above, wherein the water-insoluble dye (A) molecule and the compound (C) residue are linked via the alkylene group. Provided is a pigment derivative characterized in that

The following are mentioned as a preferable form of the pigment derivative of this invention.
The aldehyde compound (B) is at least one selected from the group consisting of paraformaldehyde, trioxane, formaldehyde, formalin, glyoxal, and alkyl aldehyde having 1 to 10 carbon atoms. The methine having an easily replaceable hydrogen group, wherein the compound (C) is selected from the group consisting of a phenol compound having 6 to 20 carbon atoms and an N, N-disubstituted aniline compound having 8 to 20 carbon atoms. A hydrocarbon compound having a group (—CH═) and a derivative thereof (C-1); The compound (C) is an amino acid compound having 1 to 10 carbon atoms, an amino compound having 1 to 20 carbon atoms, an aminotriazine compound having 0 to 10 carbon atoms, a carboamide compound having 1 to 20 carbon atoms, or a 1 to 20 carbon atom. An amino compound having a reactive amino group and a derivative thereof (C-2) selected from the group consisting of a carboimide compound (excluding phthalimide) and a sulfamic acid compound having 0 to 10 carbon atoms.

The number of compound (C) residues bonded to the water-insoluble dye (A) molecule via an alkylene group is 1 to 6. The water-insoluble pigment (A) is at least one selected from the group consisting of organic pigments, vat dyes and disperse dyes. The water-insoluble dye (A) is phthalocyanine, anthraquinone, perylene, perinone, dioxazine, quinacridone, diketopyrrolopyrrole, indigo / thioindigo, quinophthalone, isoindolinone, metal complex And at least one selected from the group consisting of insoluble azo dyes and high molecular weight azo dyes.

Further, as another embodiment, the present invention provides a liquid medium comprising any one of the above-described dye derivatives and a dilution medium, an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system, or a polymerization medium. Provided is a colorant comprising at least one of a polymerizable liquid medium comprising a polymerizable oligomer or a polymerizable monomer, or a resin medium comprising a synthetic resin. Preferred examples of such a colorant include the following forms. Furthermore, it contains a polymer system dispersant or a low molecular weight dispersion aid as a dispersion aid. For dyeing agent, printing agent, paint, printing ink, stationery, paint, resin colorant, electrophotographic printing developer, electrostatic printing developer or color filter pixel forming ink It must be either.

As another embodiment, the present invention provides a coloring method selected from dyeing, textile printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, or a color filter pixel forming method. Further, the present invention provides a method for coloring an article characterized by using any one of the above colorants.

Further, the present invention, as another embodiment, when coloring a color filter substrate by a coloring method for forming pixels by any one of a photoresist method, an inkjet printing method, a printing method, a transfer method, or a pasting method, Provided is a method for coloring an article characterized by using any of the colorants.

More specifically, in the present invention, the dye solution or dispersion (hereinafter collectively referred to as “base color”) used for the colorant is any one of the above-described dye derivatives, and further, if necessary, a pigment, an oil A liquid medium containing a soluble dye or a water-soluble dye and comprising, as a dilution medium, an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system; a polymerizable oligomer, a polymerizable liquid medium comprising a polymerizable monomer; Provided is a base color characterized in that a resin medium comprising a plasticizer, an oligomer and a synthetic resin is used, and if necessary, a polymer system dispersant and a low molecular dispersion aid are used as a dispersion aid.

In the present invention, the colorant contains any one of the above-described pigment derivatives as a colorant, and if necessary, further contains a pigment, an oil-soluble dye or a water-soluble dye. Liquid medium composed of mixed solvent system of hydrophilic organic solvent; Polymerizable liquid medium composed of polymerizable oligomer and polymerizable monomer; Resin medium composed of plasticizer, oligomer and synthetic resin, and / or containing pigment derivative One or more selected from the group consisting of a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer and a cross-linking agent using the base color and / or as a film-forming material. Provided is a colorant characterized by containing a material and further containing a curing catalyst, a polymerization catalyst and the like as required.

The present invention provides a colored article formed by a known coloring method using any one of the above-described colorants of the present invention.

According to the present invention as described above, the carbon atom of the alkylene group is linked to the carbon atom of the water-insoluble dye to form a carbon-carbon bond, and in a more preferred form, it has a hydrophilic group, so it is soluble in an aqueous medium. As a pigment, a pigment derivative excellent in light resistance as compared with a dye is provided. In addition, since the pigment derivative of the present invention provides a deep color effect depending on the number of substituents introduced, characteristics are also shown in the color tone. It is possible to provide a sky blue color excellent in fastness used in the printing / recording field, resin coloring field, etc., and is useful for various applications.

Further, according to the present invention, depending on the nature of various substituents introduced into the residue of the compound (C) linked to the water-insoluble dye (A) molecule, it is possible to suppress pigment crystal transition and crystal growth. It is possible to provide a pigment derivative that is effective as an additive. Therefore, according to the present invention, the function of a dispersion aid or the like that improves the dispersibility of the pigment of the organic solvent-based pigment dispersion color, decreases the viscosity of the dispersion, improves dispersion stability, long-term storage stability, etc. A colorant containing a sex additive is obtained. Furthermore, since these can be obtained from derivatives based on existing dye skeletons, they can be carried out economically and efficiently, and are extremely useful from a practical viewpoint.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The dye derivative of the present invention comprises a water-insoluble dye (A), an aldehyde compound (B) that reacts with the dye (A) to form an alkylene group, a compound and its derivative (C), and is water-insoluble. The dye (A) molecule and the compound (C) residue are a derivative of a dye formed by linking via the alkylene group. That is, a pigment derivative having a structure in which the residue of compound (C) capable of imparting various properties to the molecular structure of water-insoluble pigment (A) is linked by an alkylene group (carbon-carbon bond) is provided. . The compound (C) is a hydrocarbon compound having a methine group (—CH═) having an easily replaceable hydrogen group and its derivative (C-1), an amino compound having a reactive amino group and its derivative (C -2). According to the present invention, the structure of the dye derivative and the compound (C) linked to the dye molecule are configured as described above, and as described above, as a derivative based on an existing dye skeleton, In particular, it is possible to realize a pigment derivative excellent in deep color effect and characteristics without changing the basic color tone. Hereafter, the synthesis | combining method of the pigment derivative of this invention and each component to be used are demonstrated.

[Synthesis method]
The dye derivative of the present invention has a structure in which the molecular structure of the water-insoluble dye (A) and the compound (C) residue are bonded via an alkylene group that is a residue of the aldehyde compound (B). Examples of the method for synthesizing the dye derivative include the following methods.
(1) A water-insoluble dye (A), an aldehyde compound (B) which is an alkylene-forming reactive compound, and a compound (C) having an active hydrogen group capable of condensation reaction are dissolved in a reaction medium and simultaneously reacted to synthesize. Method.
(2) First, the water-insoluble dye (A) is dissolved in the reaction medium, and the aldehyde compound (B) is added and reacted to form an alkylene group on the dye. Next, a method of synthesizing the compound (C) having an active hydrogen group capable of undergoing a condensation reaction with it.
(3) The compound (C) is reacted with the aldehyde compound (B), the reaction product is optionally isolated, and an alkylene group is added to the compound (C). Next, a method in which the water-insoluble dye (A) is added or the solution is mixed and reacted to synthesize.
(4) In each of the synthesis methods (1), (2) and (3) above, the reaction in each method is carried out using the dye intermediate (A ′) as a precursor instead of the water-insoluble dye (A). Then, the dye intermediate (A ′) may be used as the dye (A).

[Water-insoluble dye (A)]
The water-insoluble dye (A) that is a constituent material of the dye derivative of the present invention will be described. As the dye (A), the molecular structure or the dye molecular structure forming the dye main body part in the produced dye derivative has a dye molecule structure that is not bonded with a hydrophilic group, in other words, a water-insoluble dye molecule structure. Use what you have. Specific examples include the molecular structure of water-insoluble pigments used as known organic pigments, vat dyes, dispersible dyes, and the like. Here, vat dyes, naphthol dyes, and the like are used by being solubilized in water as precursors at the time of dyeing, but are water-insoluble dyes in a colored state and are used in the dye (A) used in the present invention. included.

Specific examples of the water-insoluble dye molecular structure that can be used as the dye (A) in the present invention include phthalocyanine, anthraquinone, perylene, perinone, dioxazine, quinacridone, and diketopyrrolopyrrole. , Indigo / thioindigo, quinophthalone, isoindolinone, metal complex, insoluble azo, and polymer azo based dyes.

Generally, the light fastness of a dye is displayed in the class from 8th class to 1st class, or E class, VG class, G class, F class, P class. In the present invention, the water-insoluble dye (A) used as the dye matrix is generally classified into grade 6 or grade G, preferably grade 7 or grade VG, more preferably grade 8 or more, depending on the application. It is preferred that a dye of grade E or higher is selected.

Here, in the case of pigment light resistance, the pigment molecular structure with higher fastness is superior in light resistance, but in addition, the pigment molecule has a crystal structure formation and exhibits a strong pigment, and the size of the pigment particles Some of them exhibit more robustness. However, as the dye (A) used in the present invention, a pigment considered to have high fastness due to the molecular structure of the pigment provides excellent light resistance when the dye derivative of the present invention is constituted as a final form. it is conceivable that. For this reason, the molecular structure of the preferred water-insoluble dye (A) used in the present invention has a substitution position into which a linking group formed by the aldehyde compound (B) described later can be introduced and has high light resistance. Organic pigments classified as higher pigments and vat dyes having a chemical structure similar to higher pigments as the basic skeleton are preferably selected.

Examples of the water-insoluble dye (A) used in the present invention include the following. Here, “CI pigment is abbreviated as“ P ”and blue is abbreviated as“ B ”. Therefore, C.I. I. Pigment Blue is abbreviated as “PB”. Further, “G” for green, “Y” for yellow, “O” for orange, “V” for violet, and the colors are also abbreviated in the same manner. For example, PB15, aluminum phthalocyanine blue, PB16, PG7, PG36, poly (13-16) bromocopper phthalocyanine green, PG58, etc. as phthalocyanine series; PY123, PY24, PY108, bat yellow 48 (hereinafter, Vat Yellow is abbreviated as “VY”.), PO40, PR177, PR168, PB60, etc .; Per189 series, PR189, PR190, PR149, etc .; Perinone series, PO43, PR194, etc .; Dioxazine series, PV23 etc .; Quinacridone series As a diketopyrrolopyrrole system, PR254, PR255, etc .; As an indigo / thioindigo system, PR87, PV36; Like PY153 as metal complex; PY139, PY109 such as isoindolinone; etc. PY138 is Te. Furthermore, a coloring compound having a chemical structure similar to the above-mentioned higher-class pigments as a basic skeleton can also be used.

[Aldehyde compound (B)]
The aldehyde compound (B) which is a constituent material of the pigment derivative of the present invention will be described. The aldehyde compound (B) can react with the dye (A) to form an alkylene group. Specifically, in the first stage addition reaction, a hydroxyl group such as a methylol group, an alkoxymethyl group, or a halogenomethyl group or a reactive derivative group thereof is formed, and then the second stage dehydration, dealcoholization, A compound in which the water-insoluble dye (A) described above and a compound (C) residue described below are linked via an alkylene group by a condensation reaction such as dehydrohalogenation. Examples of the aldehyde compound (B) include formaldehyde, trioxane, paraformaldehyde, formalin, glyoxal, or an alkyl aldehyde having 1 to 10 carbon atoms. Of these, paraformaldehyde is particularly preferable.

[Compound (C)]
The compound (C) which is a constituent material of the pigment derivative of the present invention will be described. In the present invention, the compound (C) is selected from the group consisting of the following compounds and derivatives.
(1) Hydrocarbon compound having a methine group (—CH═) having an easily replaceable hydrogen group and its derivative (C-1)
(2) Amino compounds having a reactive amino group and derivatives thereof (C-2)

Since the methine group of the hydrocarbon compound having a methine group in (C-1) has an easily replaceable hydrogen group, it is formed from the aldehyde group of the aldehyde compound (B) described above or the aldehyde compound (B). It can be dehydrated with a hydroxyl group such as a methylol group to form a bond. Examples of the hydrocarbon compound having a methine group include a hydrocarbon group having an easily replaceable hydrogen atom of an aromatic skeleton. Specific examples include phenol compounds (carbon number: 6-20) and N, N-disubstituted aniline compounds (carbon number: 8-20), which are preferably used.

Preferred amino compounds having a reactive amino group in the above (C-2) are amino acid compounds (carbon number: 1 to 10), amino compounds (carbon number: 1 to 20), aminotriazine compounds (carbon number: 0-10), carboamide compounds (carbon number: 1-20), carboimide compounds having 1-20 carbon atoms (excluding phthalimide), sulfamic acid compounds (carbon number: 0-10), and the like. Also with these compounds, bonds can be formed by a dehydration reaction as in the case of the above-mentioned compound (C-1).

(Substituent)
It is preferable that a known substituent is introduced into the compound (C-1) selected from the compounds (C-1) and (C-2) described above and derivatives thereof. The substituent becomes a substituent of the residue of the compound (C), and can provide performances such as various properties, functions and physical properties to the dye derivative of the present invention. The substituent is selected from, for example, the following hydrophilic group group, lipophilic group group, and reactive group group.

<Group of hydrophilic groups>
Any anionic group selected from a carboxyl group, a sulfonic acid group, a phosphate ester group and a sulfate ester group;
-Alkali metal salts, ammonium salts, (mono, di, tri) -alkylamine salts, (mono, di, tri) -alkanolamine salts, (mono, di, tri)-(polyoxy) of these anionic groups A salt of any anionic group selected from (alkylene) oxyalkylamine salts;
Any cationic group selected from a tertiary amino group and a quaternary ammonium group;
A salt of any one of these cationic groups selected from a halogenate, a sulfonate, and an alkyl carboxylate;
Any nonionic group selected from a polyalcohol group and a polyethylene glycol group;

<Group of lipophilic groups>
Any group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and a halogen group <reactive group group>
Any group selected from the group consisting of a glycidyl group, a methylol group, and an alkoxy (carbon number: 1 to 4) methyl group;

(Hydrocarbon compound (C-1))
Next, the hydrocarbon compound (C-1) having a methine group (—CH═) having an easily replaceable hydrogen group described above is specifically shown below. As a phenol compound suitable as a hydrocarbon compound having an easily replaceable hydrogen atom of an aromatic skeleton, a reactive phenol compound having an active hydrogen group at the o-position or p-position of a hydroxyl group or an equivalent position thereof is preferable. . Specific examples include aromatic hydrocarbons having 6 to 20 carbon atoms having a phenolic hydroxyl group and heterocyclic compounds. For example, known phenol compounds (hydroxybenzenes), naphthols, hydroxycarbazoles and the like having one to a plurality of hydroxyl groups (such as 4) in the molecule are suitable.

Particularly preferred phenolic compounds in the present invention include, when reacted with the dye (A) and the aldehyde compound (B), the substituent is at the o-position or p-position of the phenolic hydroxyl group or the equivalent position thereof. Are introduced so as to leave an active hydrogen group. For example, the following are mentioned. Examples of phenols having an alkyl group as a substituent include 2-t-butyl-4-methylphenol, 2-t-butyl-6-methylphenol, 2,3 as amphiphilic nonpolar phenols. , 6-trimethylphenol, 2-methyl-5-isopropylphenol, 3-methyl-4-isopropylphenol, 5-methyl-2-isopropylphenol, etc .; as ionic phenols, o-cresol-4-sulfonic acid, Examples include 3-methyl salicylic acid, 4-methyl salicylic acid, 5-methyl salicylic acid and the like. In particular, in order to produce a single dye derivative having a controlled structure and a structure, a compound substituted so that there is one active hydrogen group at the o-position or p-position is preferred.

Furthermore, the above phenolic hydroxyl group can be subsequently etherified with an alkyl halide or an epoxy compound. Examples of the ether group formed at this time include an alkyl ether group, an alkyl (hydroxy) propyl ether group, an alkoxy (hydroxy) propyl ether group, a phenyl ether group, and a phenoxy (hydroxy) propyl ether group.

Examples of suitable hydrocarbon compounds having easily replaceable hydrogen atoms with an aromatic skeleton other than the above-described phenol compounds include N, N-disubstituted aniline compounds. For example, it is preferable to use N, N-dialkylaniline, N, N-dialkanolaniline, or the like.

(Amino compound having a reactive amino group (C-2))
Specific examples of the amino compound (C-2) having a reactive amino group used in the present invention that can be suitably used are shown below. Examples of the amino acid compound having 1 to 10 carbon atoms include glutamic acid, aspartic acid, taurine, N-methyl taurine and the like. Examples of the amino compound having 1 to 20 carbon atoms include N, N-dimethylethylenediamine, N, N-diethyl-1,3-diaminopropane, N, N-diethyl 1,4-diaminopentane, diethanolamine, and diisopropanolamine. N, N, N′-trimethylethylenediamine, N, N, N′-triethylethylenediamine and the like. Examples of the aminotriazine compound having 0 to 10 carbon atoms include 2-amino-4,6-dihydroxy-s-triazine, 2-amino-4,6-dipropylamino-s-triazine, 2-amino- Examples include 4,6-carboxymethylamino-s-triazine, 2-amino-4,6-dicarboxymethylamino-s-triazine, and the like.

Examples of the carbonamide compound having 1 to 20 carbon atoms include acetamide, propioamide, butyramide, octanamide, stearamide, trimellitic acid monoamide, sulfosuccinic acid monoamide, and the like, and nitriles that are amidated when used in sulfuric acid, for example, Examples include acetonitrile, octonitrile, stearonitrile, and benzonitrile. Specific examples of carboimide compounds (excluding phthalimide) suitable for the present invention include trimellitic imide, sulfosuccinimide, o-sulfobenzimide and the like. Examples of the sulfamic acid compound include sulfamic acid.

[Reaction medium]
The dye derivative of the present invention is obtained by reacting the water-insoluble dye (A), the aldehyde compound (B) and the compound (C) described above. The reaction medium used in that case will be described. A reaction medium suitable for the present invention is a medium in which the water-insoluble dye (A) is dissolved. The organic pigments and vat dyes which are the preferred colorants (A) of the present invention mentioned above do not dissolve in ordinary organic solvents, so 95% to 100% highly concentrated sulfuric acid, fuming sulfuric acid, polyphosphoric acid, etc. are used. Is done. Then, the reaction product obtained from the components (A), (B) and (C) described above is poured into a large amount of water, ice water or ice in accordance with a conventional method from a sulfuric acid solution, etc. What is necessary is just to filter and wash with water. At this time, it is washed with a weakly acidic aqueous hydrochloric acid solution depending on the properties of the pigment derivative.

The dye derivative of the present invention has a color tone and lyophilicity depending on the nature of the compound (C) residue bonded to the molecular structure of the water-insoluble dye (A) via an alkylene group and the number of residues to be introduced. Since the properties change, it is preferable to determine the setting and the number of introduced compounds (C) via an alkylene group (for example, a methylene group) so that the target dye derivative is synthesized. The number of bonds (number) of the compound (C) residue is not particularly limited, but is about 1 to 6. When used as a water-soluble dye, it is necessary to be able to bring about water solubility, and it is preferable to introduce approximately 2 or more, preferably 3 or more.

When the pigment derivative of the present invention is used as a water-soluble dye, the substituent of the compound (C) residue of the pigment derivative is preferably in the form of a salt. For example, when the substituent is an anionic group comprising a carboxyl group, a sulfonic acid group, a phosphoric ester group, or a sulfuric ester group, an alkali metal salt such as a sodium salt or a potassium salt of the anionic group; an ammonium salt; (Mono, di, tri) ethylamine salts, (mono, di, tri) alkylamine salts such as propylamine salts; (mono, di, tri) ethanolamine salts, (mono, di, tri) ) (Mono, di, tri) alkanolamine salts such as propanolamine salts; (mono, di, tri)-(polyoxyalkylene) oxyalkylamine salts such as (mono, di, tri) (polyethyleneoxyethyl) amine salts It is preferable to use in the form. In addition, when the substituent is a cationic group composed of a tertiary amino group or a quaternary ammonium group, for example, a halogen salt such as hydrochloride of the cationic group; an alkyl such as acetic acid or propionate Carboxylic acid salt; It is preferably a hydrophilic group such as a hydroxyalkyl carboxylate such as glycolate or lactate.

As described above, in the dye derivative of the present invention, the alkylene group in which the compound (C) residue formed by the aldehyde compound (B) and the compound (C) is bonded to the molecular structure of the original dye is bonded as a substituent. Configured. For this reason, the pigment derivative of the present invention has an effect of deepening the original color tone of the water-insoluble pigment (A) (shifting the absorption wavelength to the longer wavelength side). For example, in the molecular structure of copper phthalocyanine, the number of the above-mentioned substituents (alkylene group to which the compound (C) residue is bonded) shifts to greenish blue particularly when it is 2 or more, which is desired in the image recording field such as inkjet printing Cyan to sky blue colors that are characteristic of being obtained. The number of substituents in the present invention means the number of compound (C) residues bonded through an alkylene group.

[Colorant]
When the dye derivative of the present invention described above is used as a colorant, the dye derivative of the present invention can be used in various fields by diluting it with various dilution media suitable for various applications. Thus, simpler use is possible. That is, the colorant of the present invention is a liquid medium composed of any one of an organic solvent system, an aqueous system, or a water-hydrophilic organic solvent mixed solvent system, or a polymerizable oligomer or polymerized polymer. It is characterized by containing at least one of a polymerizable liquid medium made of a polymerizable monomer or a resin medium made of a synthetic resin. For example, the base color (pigment solution or dispersion) constituting the colorant of the present invention contains the pigment derivative of the present invention and, if necessary, other pigments, oil-soluble dyes or water-soluble dyes as a medium. The above-described liquid medium, polymerizable liquid medium, and resin medium may be used, and if necessary, the dispersion aid may be further used with a polymer system dispersant or a low molecular dispersion aid.

In addition, when the pigment is used in the production of the pigment or in the use of the organic solvent dispersion type colorant or the colorant for plastics, the dye derivative of the present invention has the pigment crystal transition inhibition, crystal growth inhibition, and dispersibility. It can also be added and used for the purpose of improving the heat resistance. In particular, the pigment derivative of the present invention added to a pigment crude (coarse pigment) or a coarse particle pigment to form a pigment composition is effective for the post-treatment (pigmenting treatment) of the pigment. This dye derivative brings an excellent effect in improving the dispersion performance of the liquid dispersion color of the pigment and improving the storage stability. When used as a pigment crystal growth inhibitor or a dispersion stabilizing aid, it is desirable that the pigment is insoluble in an organic solvent medium. For this reason, an oleophilic group is introduced as a substituent of the aforementioned compound (C) residue, and the oleophilic group is approximately 1 or less, preferably an average number relative to the entire pigment including the pigment derivative. Those into which 0.5 to 0.1 lipophilic groups are introduced are preferably used. On the other hand, when a color filter pixel forming ink or a solvent-based colorant is used, in addition to the pixel forming pigment, the film forming material, and the dilution medium, the dye derivative of the present invention having the above ionic group, and its It is preferable to use a philic polymer having a counter ionic group as a pigment dispersant.

In the dye derivative-containing composition using the dye derivative of the present invention as mentioned above, the dye component is contained in a high concentration, and the dye derivative or other dye used in combination is dissolved or finely dispersed in advance. The production of the colorant can be facilitated. The dye derivative-containing composition using the dye derivative of the present invention contains a dye derivative and other dyes as required in accordance with the intended colorant formulation, and an organic solvent, water or water as a medium. -Liquid medium composed of mixed solvent system of hydrophilic organic solvent; Polymerizable liquid medium composed of polymerizable oligomer and polymerizable monomer; Resin medium composed of plasticizer, oligomer and synthetic resin, dispersed as required It can be prepared by containing a polymer system dispersing agent and a low molecular weight dispersing aid as an auxiliary agent.

The colorant containing the pigment derivative of the present invention is a dyeing agent, a printing agent, a paint, a printing ink, a stationery, a paint, a resin colorant, and various information technology-related colorants, for example, for color resists used in the production of color filters It can be applied as a colorant, a liquid colorant such as a liquid developer for an electrophotographic printer, or a dry developer for an electrophotographic printer. Then, they are used for known coloring methods such as dyeing, textile printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, and color filter pixel forming methods.

The colorant of the present invention contains the pigment derivative of the present invention, and, if necessary, other pigments such as other pigments, oil-soluble dyes, water-soluble dyes, etc. It is prepared by adding one or more materials selected from thermoplastic polymers, reactive polymers, reactive oligomers, polymerizable monomers, crosslinking agents, and the like as the coating film forming material. If necessary, the colorant of the present invention may further include a curing catalyst, a polymerization catalyst, or the like. Alternatively, the above-described dye derivative-containing composition may be used, and the necessary materials described above may be further added to dissolve, mix, It can be prepared by adding necessary processing according to the application such as dispersion.

As the resin to be added as a film forming material used in the above, known resin components corresponding to the respective applications are used. For example, known coating film forming materials such as synthetic rubber resin, acrylic resin, vinyl resin, chlorinated rubber resin, alkyd resin, urethane resin, epoxy resin, silicone resin, fluororesin, and ultraviolet curable resin system, electron beam curable Examples include resin-based energy ray-curable coating film forming materials. The coating film forming material may or may not have a reactive group. Examples of the reactive group include a methylol group, an alkylmethylol group, an isocyanate group, a masked isocyanate group, and an epoxy group. Can be mentioned. In addition, oligomers and monomers are used depending on the application, and a cross-linking agent such as methylol melamine type, isocyanate type, and epoxy type cross-linking agent is also used in combination. In the colorant described above, the blending mass ratio of the pigment (P) and the coating film forming material (V) can be arbitrarily determined depending on the application, required performance, etc., but P: V = 80: 20 to 1:99, preferably 70:30 to 10:90.

The material or article colored by the colorant of the present invention is determined by the purpose and application of coloring, and conventionally known materials and articles are targeted. For example, coloring compositions for image recording such as digital laser printers and full-color toners for full-color copiers, and examples of articles to be colored with the composition include paper, synthetic paper, non-woven paper, and plastic films. It is done.

When the colorant of the present invention is used for forming a color filter pixel, a colorant suitable for the formation method is used, and a known photoresist method, printing method, transfer method, and pasting are performed on the color filter substrate. Pixels are formed by the method. In a coloring composition for image display such as a color filter for a liquid crystal display and an advertising display, examples of the coloring object of the composition include a glass substrate and a plastic plate substrate.

Next, the present invention will be described in more detail with specific production examples and examples. In addition, the part and% in a sentence are based on mass unless there is particular notice.

[Production Example 1: Synthesis of ε-type copper phthalocyanine pigment for color filter]
(1-1) (Synthesis of anionic pigment in which sulfonic acid is introduced into pigment)
A reactor equipped with an electric heater, a stirrer, a reagent inlet and a back-flow cooler as a heating device was charged with 120 g of sulfuric anhydride, and 5.76 g of copper phthalocyanine blue pigment (MW (molecular weight): 576) was added while stirring. 01 mol) was added and dissolved. Thereafter, the mixture was heated to 50 ° C., 0.60 g (0.02 mol) of paraformaldehyde (MW: 30 (monomer)) was added, stirred for 1 hour and 30 minutes, and reacted to synthesize a methylol form.

Next, the temperature was raised to 80 ° C., 3.76 g (0.02 mol) of o-cresol-4-sulfonic acid (MW: 188.2, purity 86%) was added in a pure amount, and 80 ° C. to 85 ° C. For 6 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature and precipitated in about 1,000 ml of ice water. The precipitated reaction product was filtered, washed with water and dried. Thereafter, the soluble component was removed by washing with acetone to obtain o-cresol-4-sulfonic acid (-6-) methylated copper phthalocyanine. The number of substitution is approximately 0.5. Hereinafter, this is referred to as “blue dye derivative-1”. Table 1 summarizes the composition.

(1-2) (Preparation of ε-type copper phthalocyanine pigment)
100 parts of α-type copper phthalocyanine, 1 part of the blue pigment derivative-1 obtained above, 3 parts of phthalimidomethyl copper phthalocyanine, 10 parts of ε-type copper phthalocyanine blue pigment (CI Pigment Blue 15: 6), salt 300 parts and 110 parts of diethylene glycol were ground in a kneader for 20 hours while maintaining the temperature of the contents at 100-110 ° C.
The obtained content is heat-treated in a 2% dilute sulfuric acid solution to dissolve soluble components such as salt, and the treated pigment is filtered, washed with water, and a press composition of a pigment composition containing copper phthalocyanine as a main component Got. The copper phthalocyanine obtained above was confirmed to be ε-type by X-ray diffraction.

(1-3) (Preparation of blue pigment composition)
Further, the press cake of the pigment composition containing the ε-type copper phthalocyanine and the press cake of the blue pigment derivative-1 obtained in (1-1) were blended so as to have a solid content of 91: 9, Water was added and peptized with a homomixer to obtain a 5% aqueous suspension. After stirring for 1 hour, filtration, washing with water, drying and pulverization were performed to obtain a reddish blue pigment composition containing ε-type copper phthalocyanine as a main component. Hereinafter, this is referred to as “blue pigment composition-1”. Table 2 summarizes the composition.

[Comparative Production Example 1: Preparation of comparative blue pigment composition]
Ε-type copper phthalocyanine pigment is included as a main component in the same manner as in Production Example 1-3, except that a known monosulfonated copper phthalocyanine is used instead of the blue pigment derivative-1 used in Production Example 1-3. A comparative blue pigment composition was prepared. Hereinafter, this is referred to as “comparative blue pigment composition-1”. Table 2 shows the composition.

[Production Example 2: Production of ε-type copper phthalocyanine pigment for color filter]
(2-1) (Synthesis of anionic pigment with sulfonic acid introduced into pigment)
Similar to Production Example 1-1 except that 2.09 g (0.015 mol) of N-methyltaurine (MW: 139) was used instead of o-cresol-4-sulfonic acid used in Production Example 1-1. Thus, N-methyl-N- (sulfoethyl) aminomethylated copper phthalocyanine was obtained. The number of substitution is approximately 0.4. Hereinafter, this is referred to as “blue dye derivative-2”. Table 1 summarizes the composition.

(2-2) (Preparation of blue pigment composition)
In Production Example 1-3, the blue pigment derivative-2 obtained above was used in place of the blue pigment derivative-1 used, and the production process was carried out in the same manner, and redness containing ε-type copper phthalocyanine as the main component. A blue pigment composition was obtained. Hereinafter, this is referred to as “blue pigment composition-2”. Table 2 summarizes the composition.

[Production Example 3: Production of ε-type copper phthalocyanine pigment for color filter]
(3-1) (Synthesis of anionic pigment with sulfonic acid introduced into pigment)
In the same manner as in Production Example 1-1, except that 1.46 g (0.015 mol) of sulfamic acid (MW: 97) was used instead of o-cresol-4-sulfonic acid used, sulfoamidomethylation was performed. Copper phthalocyanine was obtained. The number of substitution is approximately 0.4. Hereinafter, this is referred to as “blue dye derivative-3”. Table 1 summarizes the composition.
(3-2) (Preparation of blue pigment composition)
In Production Example 1-3, the blue dye derivative-3 obtained above was used instead of the blue pigment derivative-1 used, and the production process was similarly carried out to obtain a reddish blue color containing ε-type copper phthalocyanine as a main component. A pigment composition was obtained. Hereinafter, this is referred to as “blue pigment composition-3”. Table 2 summarizes the composition.

[Production Example 4: Introduction of hydrophobic group, synthesis of pigment with improved hue]
To 120 g of anhydrous sulfuric acid, 9.20 g (0.06 mol) of caprinonitrile (MW: 153.3) and 2.25 g (0.075 mol) of paraformaldehyde are added, dissolved, and reacted to synthesize a methylol body. Next, 6.04 g (0.01 mol) of a dimethyl copper phthalocyanine pigment having an average of 2 methyl groups in the molecule (average molecular weight: 604) was added, and the mixture was reacted at 80 ° C. to 85 ° C. for 6 hours with stirring. The mixture was cooled to room temperature, precipitated in approximately 1,000 ml of ice water, filtered, washed with water, and dried. The soluble component was removed by washing with acetone to obtain caprinamide methylated dimethyl copper phthalocyanine. The number of caprinamidomethyl groups substituted is approximately 3.1. Hereinafter, this is referred to as “blue dye derivative-4.” Table 1 summarizes the composition.

The above results are summarized in Table 1 and Table 2 below.

[Production Example 5: Introduction of hydrophilic group into pigment to synthesize water-soluble dye]
(5-1) (Preparation of hydrophilic dye)
In the same manner as in Production Example 1-1, 5.76 g (0.01 mol) of copper phthalocyanine blue pigment was added to 130 g of sulfuric anhydride and dissolved, and then 2.25 g (0.075 mol) of paraformaldehyde was added. And stirred for 20 minutes. Trimellitic acid imide (MW: 191) (11.46 g, 0.06 mol) was added, heated, and reacted by stirring at 80 ° C. to 85 ° C. for 6 hours. The mixture was cooled to room temperature, precipitated in approximately 1,000 ml of ice water, filtered, washed with water, and dried. The soluble matter was removed by washing with acetone to obtain trimellitic acid imidomethylated copper phthalocyanine which is a pigment derivative of the present invention. The number of substitution is approximately 3.2.

(5-2) (Preparation of hydrophilic dye solution: Method using sodium hydroxide)
Next, 12.26 g of trimellitic acid imidomethylated copper phthalocyanine obtained above was stirred and dispersed in 100 g of water. 12.8 g of a 20% aqueous sodium hydroxide solution was added, and the mixture was heated to 50 ° C. and stirred for 30 minutes to saponify and dissolve. Further, the pH was adjusted to 8 with a 1% aqueous sodium hydroxide solution, the insoluble matter was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of trimellitic acid amidomethylated copper phthalocyanine sodium salt was obtained. Hereinafter, this is referred to as “blue dye derivative-5 aqueous solution”.

(5-3) (Preparation of red and yellow solutions)
Similarly, instead of copper phthalocyanine blue pigment, a bisaminoanthraquinone red pigment (CI Pigment Red 177) is reacted to give a 10% aqueous solution of sodium salt of trimellitic acid monoamidomethyl derivative of bisaminoanthraquinone. Got. Hereinafter, it is referred to as “red pigment derivative-1 aqueous solution”.

Similarly, a flavanthrone yellow pigment (CI Pigment Yellow 24) was reacted to obtain a 10% aqueous solution of a sodium salt of trimellitic acid monoamidomethyl derivative. Hereinafter, this is referred to as “yellow pigment derivative-1 aqueous solution”.

(5-4) (Preparation of hydrophilic dye solution: ethanolamine method)
In the above, each pigment derivative aqueous solution saponified with sodium hydroxide aqueous solution was acidified with dilute hydrochloric acid aqueous solution to precipitate pigment derivative carboxylic acid and filtered to obtain a mud. A 20% ethanolamine aqueous solution was added thereto for neutralization, and the pH was adjusted to 8. Thereafter, the insoluble matter was filtered off, and water was added to prepare a 10% aqueous solution, thereby obtaining a 10% aqueous solution of an ethanolamine salt of trimellitic acid amidomethyl derivative. Hereinafter, they are referred to as “blue pigment derivative-5-2 aqueous solution”, “red pigment derivative-1-2 aqueous solution”, and “yellow pigment derivative-1-2 aqueous solution”, respectively. The above results are summarized in Table 3 below.

[Production Example 6] (A hydrophilic group is introduced into a pigment to synthesize a water-soluble dye)
(6-1) (Preparation of hydrophilic dye solution)
In the same manner as in Production Example 5-1, instead of trimellitic imide, 8.82 g (0.06 mol) of glutamic acid was used for reaction, precipitated in ice water, filtered, washed with water, dried and then washed with acetone. Thus, the soluble component was removed, and glutaric acid-1-iminomethylated copper phthalocyanine was obtained. The number of substitutions is approximately 3.1. Hereinafter, this is referred to as “blue pigment derivative-6”. Table 4 summarizes the composition.

(6-2) (Preparation of hydrophilic dye solution: Method using sodium hydroxide)
In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, adjusted to pH 8, the insoluble matter was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of sodium salt of glutaric acid-1-iminomethylated copper phthalocyanine was obtained. Hereinafter, this is referred to as “blue dye derivative-6 aqueous solution”.

[Production Example 7] (A hydrophilic group is introduced into a pigment to synthesize a water-soluble dye)
(7-1) (Preparation of hydrophilic dye solution)
In the same manner as in Production Example 5-1, the reaction was carried out using 8.34 g (0.06 mol) of N-methyltaurine in place of trimellitic imide, precipitated in ice water, filtered, washed with water, dried, The soluble component was removed by washing with acetone to obtain N- (sulfoethyl) -N-methylaminomethylated copper phthalocyanine. The number of substitution is approximately 3.2. Hereinafter, this is referred to as “blue dye derivative-7”. Table 4 summarizes the composition.

(7-2) (Preparation of hydrophilic dye solution: Method using sodium hydroxide)
In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, adjusted to pH 8, the insoluble matter was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of sodium salt of N-methyl-N- (sulfoethyl) aminomethylated copper phthalocyanine was obtained. Hereinafter, this is referred to as “blue dye derivative-7 aqueous solution”.

[Production Example 8] (A hydrophilic group is introduced into a pigment to synthesize a water-soluble dye)
(8-1) (Preparation of hydrophilic dye solution)
In the same manner as in Production Example 5-1, the reaction was carried out using 5.82 g (0.06 mol) of sulfamic acid (MW: 97) instead of trimellitic acid imide, and the mixture was precipitated in ice water, filtered, washed with water, Soluble components were removed to obtain sulfoamidomethylated copper phthalocyanine. The number of substitutions is approximately 3.3. Hereinafter, this is referred to as “blue pigment derivative-8”. Table 4 summarizes the composition.

(8-2) (Preparation of hydrophilic dye solution: Method using sodium hydroxide)
In the same manner as in Production Example 5-2, the mixture was dispersed in water, neutralized with an aqueous sodium hydroxide solution, adjusted to pH 8, the insoluble matter was filtered off, and water was added to adjust to a 10% aqueous solution. A 10% aqueous solution of a sodium salt of sulfoamidomethylated copper phthalocyanine was obtained. Hereinafter, this is referred to as “blue dye derivative-8 aqueous solution”.

[Example 1: Preparation of dispersion]
(1-1) (Preparation of blue pigment dispersion-1)
Blue pigment composition-1 (reddish blue pigment composition containing ε-type copper phthalocyanine as a main component) obtained in Production Example 1-3, benzyl methacrylate-methacrylic acid-2-hydroxyethyl methacrylate copolymer ( Molar ratio: 60:20:20, weight average molecular weight 30,000) (hereinafter referred to as “BzMA-MAc-HEMA copolymer”) 30 parts, cyclohexanone 100 parts and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMA) ) 60 parts Dispersic-163 (by Big Chemie: solid content 45%) 66.7 parts were premixed with a paint conditioner. Thereafter, 143.3 parts of PGMA was added so that the pigment concentration was 20%, and the mixture was dispersed with a continuous horizontal medium disperser to obtain a blue pigment dispersion. Hereinafter, this is referred to as “blue pigment dispersion-1”.

(1-2) (Preparation of Comparative Blue Pigment Dispersion-1)
Except for using the comparative blue pigment composition-1 obtained in Comparative Production Example 1 (including a known ε-type copper phthalocyanine pigment using a monosulfonated copper phthalocyanine as a main component), Example 1-1 Similarly, “Comparative Blue Pigment Dispersion-1” was prepared.

<Evaluation: Comparison of color tone of blue pigment dispersion>
The color tones of Blue Pigment Dispersion-1 obtained above and Comparative Blue Pigment Dispersion-1 were compared. Blue Pigment Dispersion-1 using Blue Pigment Composition-1 is a reddish blue than Comparative Blue Pigment Dispersion-1 using Comparative Blue Pigment Composition-1 (monosulfonated copper phthalocyanine). Met.

[Example 2: Application to glass substrate]
(2-1) (Preparation of blue glass substrate)
A glass substrate was set on a spin coater, and the blue pigment dispersion liquid-1 obtained in Example 1 was dropped, and spin coating was initially performed at 300 rpm for 5 seconds and then at 1,200 rpm for 5 seconds. Subsequently, prebaking was performed at 90 ° C. for 2 minutes, and further post-baking was performed at 230 ° C. for 30 seconds to prepare a blue coated glass substrate-1. Hereinafter, this is referred to as “blue coated glass substrate-1”.

(2-2) (Preparation of a blue coated glass substrate for comparison)
Using comparative blue pigment dispersion-1 of ε-type copper phthalocyanine pigment using the monosulfonated copper phthalocyanine obtained in Example 1, it was coated in the same manner as in (2-1) above, and a comparative blue coated glass substrate -1 was prepared. Hereinafter, it is referred to as “comparative blue coated glass substrate-1”.

<Evaluation: Evaluation and comparison of optical properties of blue coated glass substrate>
The optical properties of the blue coated glass substrate-1 produced above and the comparative blue coated glass substrate-1 were evaluated. A color analyzer TC-1800MK2 (manufactured by Tokyo Denshoku Co., Ltd.) was used as the chromaticity meter. The light at this time was auxiliary standard illuminant C.
As a result, the blue coated glass substrate-1 using the blue pigment dispersion-1 showed a maximum transmission wavelength of 458 nm and a Y value of 17.6. On the other hand, the comparative blue coated glass substrate-1 using the comparative blue pigment dispersion-1 having monosulfonated copper phthalocyanine showed a maximum transmission wavelength of 461 nm and a Y value of 17.0. The glass substrate using the pigment derivative of the present invention shows a reddish blue color compared to the glass substrate using the monosulfonated copper phthalocyanine as a comparison, and the maximum transmission wavelength is on the short wavelength side. The dye derivative was more reddish blue. Moreover, it was confirmed that the dye derivative of the present invention has a high Y value.

[Example 3: Application to color filter]
(3-1) (Preparation of blue pigment dispersion)
In the same manner as in Example 1-1, 20 parts of the blue pigment composition-1 obtained in Production Example 1-2, 2 parts of BzMA-MAc-HEMA copolymer, 13.3 parts of Dispersic-163, and 64.7 parts of PGMA was premixed with a paint conditioner and then dispersed with a continuous horizontal medium disperser to obtain a blue pigment dispersion using the dye derivative of the present invention. Hereinafter, this is referred to as “blue pigment dispersion-2”. The blue pigment fine dispersion obtained here was excellent in storage stability without thickening at 45 ° C. for 1 week. The composition is shown in Table 5.

Further, as shown in Table 5, instead of the blue pigment composition-1 used in the above, the “blue pigment dispersion-3” using the blue pigment composition-2 obtained in Production Example 2-2. Were prepared using the blue pigment composition-3 obtained in Production Example 3-2, respectively.

(3-2) (Preparation of pigment dispersions of green, red, yellow and purple)
In the same manner as in the above (3-1), green, red, yellow and purple pigment dispersions used for the resist ink were prepared. Specifically, in place of the blue pigment composition-1 used in (3-1), PG36 (copper phthalocyanine green pigment), PR254 (diketopyrrolopyrrole red pigment), PR177 (aminoanthraquinone red pigment), PY150 (Nickel Complex Yellow Pigment) and PV23 (Dioxazine Violet Pigment), each pigment composition having a known pigment derivative added thereto, each having a pigment content of 20% in the same manner as in (3-1) above. A pigment dispersion was obtained. These are hereinafter referred to as “green pigment dispersion-1”, “red pigment dispersion-1”, “red pigment dispersion-2”, “yellow pigment dispersion-1”, “purple pigment dispersion-1”, respectively. Called.

(3-3) (Preparation of photosensitive resist ink for each pigment)
In order to form red (R), green (G), and blue (B) pixels on the glass substrate of the color filter, photosensitive blue resist inks 1, 2, 3, Photosensitive green resist ink and photosensitive red resist ink were obtained.

(3-4) (Formation of RGB pixels for color filter)
The glass substrate was set on a spin coater, and the above-described photosensitive red resist ink was first spin-coated at 300 rpm for 5 seconds and then at 1,200 rpm for 5 seconds. Subsequently, prebaking was performed at 80 ° C. for 10 minutes, and a photomask having a mosaic pattern was exposed on the coated surface of the glass substrate with a super high pressure mercury lamp at a light amount of 100 mJ / cm ² using a proximity exposure machine. Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.
Subsequently, a green mosaic pattern and a blue mosaic pattern were formed by applying and baking according to the above method using the photosensitive green resist ink and the photosensitive blue resist ink in Table 6, and RGB color filters were formed. Obtained.
The obtained color filter has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and excellent light transmission properties, and is excellent as a color filter for liquid crystal color displays. Showed the nature.

[Example 4: Preparation of electrophotographic developer for digital printing and digital electronic printing]
(4-1) (Preparation of high pigment content resin composition)
30 parts of “Blue Dye Derivative-4” obtained in Production Example 4 is a polyester resin of bisphenol A-bis (propylene glycol ether) and terephthalic acid (average molecular weight: about 15,000) (hereinafter simply referred to as a polyester resin). 70 parts and two rolls were kneaded to prepare a blue pigment polyester masterbatch (resin composition containing a high pigment concentration) (hereinafter referred to as a blue masterbatch).

Similarly, 30 parts each of PR-122 (dimethylquinacridone pigment), PY-74 (monoazo yellow pigment), and PBK-7 (carbon black pigment) were kneaded with 70 parts of the above polyester resin, and red, yellow, A black polyester masterbatch was obtained. Hereinafter, they are referred to as a red master batch, a yellow master batch, and a black master batch, respectively.

(4-2) (Preparation of coloring composition for image recording and printing of full-color electrophotography)
In accordance with the formulation shown in Table 7 below, the polyester masterbatch of each color obtained above, the polyester resin and the chromium complex salt negative charge control agent were kneaded according to a conventional method. After cooling, coarsely pulverized, finely pulverized with a jet mill, and passed through a classifier to obtain a fine powder of a coloring composition for image recording having a size of 5 to 7 μm. Thereafter, colloidal silica as a fluidizing agent was added and mixed with the magnetic iron powder of the carrier to obtain a cyan, magenta, yellow and black electrophotographic dry developer. Electronic printing was performed with an electrophotographic full-color laser printer. A clear full-color electrophotographic print having the characteristic that the cyan color is a greenish cyan color was obtained.

[Example 5: Printing with water-based printing ink]
(5-1) (Preparation of aqueous gravure ink coating agent)
50 parts of polyurethane-based aqueous resin (solid content 30%) containing carboxyl group obtained from carbonate-based polyol and aliphatic isocyanate, 5 parts of water-dispersed wax (solid content 30%), 15 parts of polycarbodiimide-based crosslinking agent, 1 part of a foaming agent and 9 parts of water were blended to prepare a coating vehicle base. 20 parts of each of the blue dye derivative-5 aqueous solution, red pigment derivative-1 aqueous solution, and yellow pigment derivative-1 aqueous solution obtained in Production Example 5 were added as colorants and mixed well to obtain blue, red, and yellow coating agents. Prepared. In addition, said polycarbodiimide type | system | group crosslinking agent synthesize | combined from toluylene diisocyanate, and used the O / W emulsion (20% of solid content) of the mineral terpene solution which made the terminal of polycarbodiimide the oleyl urethane.

<Evaluation>
Using the blue, red and yellow coating agents obtained above, gravure printing or flexographic printing was carried out on a plastic film or sheet such as polyvinyl chloride, polyethylene, polyester or nylon as an aqueous gravure ink to obtain a printed matter. All of the printed materials were beautiful and transparent printed materials excellent in physical properties such as weather resistance, water resistance and durability.

(5-2) (Preparation of aqueous gravure ink coating agent)
Instead of the above blue dye derivative-5 aqueous solution, red pigment derivative-1 aqueous solution, yellow pigment derivative-1 aqueous solution, the blue dye derivative-5-2 aqueous solution, red pigment derivative- obtained in Production Example (5-4) A blue, red and yellow coating agent was prepared using an aqueous solution 1-2 and a yellow pigment derivative-1-2 aqueous solution, respectively.

<Evaluation>
In the same manner as in Example (5-1), the obtained coating agent was used as an aqueous gravure ink, and gravure printing or flexographic printing was performed on the plastic film or sheet. All of the obtained printed materials were beautiful and transparent printed materials excellent in physical properties such as weather resistance, water resistance and durability.

[Example 6: Preparation, dyeing and painting of colored coating agent]
(6-1) (Preparation of colored coating agent)
Methyl methacrylate-ethyl acrylate-acrylic acid (64: 32: 4) copolymer latex (solid content 40%) 40 parts, mica 3 parts, talc 7 parts, 3% hydroxycellulose aqueous solution 10 parts, propylene glycol 1 part of monoethyl ether, 2 parts of ethylene glycol, 0.5 part of antifoaming agent, 0.5 part of preservative, 10 parts of the polycarbodiimide crosslinking agent used in Example 5 and 6 parts of water were blended to form a coating vehicle base. Was prepared.

To the obtained vehicle base, 20 parts of each of the blue pigment derivative-5 aqueous solution, the red pigment derivative-1 aqueous solution, and the yellow pigment derivative-1 aqueous solution, which are the pigment derivatives of the present invention, are added as a colorant and mixed well to obtain a blue color. Red and yellow coatings were prepared.

<Evaluation: Wooden products>
Using the blue, red, and yellow coating agents obtained above, the wood products were used alone or in combination, and each hue was painted. Since the pigment derivative of the present invention undergoes a crosslinking reaction at room temperature, the obtained coating film was excellent in physical properties such as weather resistance, water resistance and durability, and a wood product coated with beautiful colors was obtained.

<Evaluation: Other than wood products>
Similarly, using the above blue, red and yellow coating agents, textile products such as woven fabrics, non-woven fabrics, synthetic leather, artificial leather, etc. Was done. As with wood products, a beautifully colored product having excellent physical properties such as weather resistance, water resistance and durability was obtained.

(6-2) (Preparation and evaluation of blue coating agent)
In the same manner as described above, a blue coating agent was obtained using a blue dye derivative-6 aqueous solution, a blue dye derivative-7 aqueous solution, and a blue dye derivative-8 aqueous solution comprising the dye derivative of the present invention. Using the obtained coating agent, the same evaluation as described above was performed. Specifically, with the red and yellow coating agents produced above, the resulting blue coating agent was used to dye wood products, paper products, textile products, etc., and to paint metal products, plastic products, etc. . A beautifully colored product with excellent physical properties such as weather resistance, water resistance and durability was obtained.

According to the above-described pigment derivative of the present invention, the soluble pigment is excellent in light resistance as compared with the dye, and the color tone also provides a deep color effect depending on the number of substitutions, and particularly the sky blue color from the phthalocyanine pigment is suitable. Can get to. In addition, depending on the nature of the substituent of the derivative residue linked to the water-insoluble dye, pigment derivatives effective as additives for suppressing pigment crystal transition and crystal growth, and pigments of organic solvent-based pigment dispersion colors A colorant containing a functional additive such as a dispersion aid that improves the dispersibility, decreases the viscosity of the dispersion, improves dispersion stability, long-term storage stability, and the like can be obtained. Since these can be obtained from derivatives based on existing dye skeletons, they can be carried out economically and efficiently.

Claims (13)

1. A water-insoluble pigment derivative used as a colorant,
   A water-insoluble dye (A);
   An aldehyde compound (B) capable of reacting with the water-insoluble dye (A) to form an alkylene group;
   Selected from the group consisting of a hydrocarbon compound having a methine group (—CH═) having an easily replaceable hydrogen group and its derivative (C-1), an amino compound having a reactive amino group and its derivative (C-2) A reaction with any compound (C);
   A dye derivative, wherein the water-insoluble dye (A) molecule and the compound (C) residue are linked to each other via the alkylene group.
2. The dye derivative according to claim 1, wherein the aldehyde compound (B) is at least one selected from the group consisting of paraformaldehyde, trioxane, formaldehyde, formalin, glyoxal, and alkyl aldehyde having 1 to 10 carbon atoms.
3. The methine having an easily replaceable hydrogen group, wherein the compound (C) is selected from the group consisting of a phenol compound having 6 to 20 carbon atoms and an N, N-disubstituted aniline compound having 8 to 20 carbon atoms. The dye derivative according to claim 1 or 2, which is a hydrocarbon compound having a group (-CH =) and a derivative thereof (C-1).
4. The compound (C) is an amino acid compound having 1 to 10 carbon atoms, an amino compound having 1 to 20 carbon atoms, an aminotriazine compound having 0 to 10 carbon atoms, a carboamide compound having 1 to 20 carbon atoms, or a 1 to 20 carbon atom. The amino compound having a reactive amino group and a derivative thereof (C-2) selected from the group consisting of a carboimide compound (excluding phthalimide) and a sulfamic acid compound having 0 to 10 carbon atoms. 2. The pigment derivative according to 2.
5. The dye derivative according to claim 1 or 2, wherein the number of the compound (C) residues bonded to the water-insoluble dye (A) molecule via an alkylene group is 1 to 6.
6. The pigment derivative according to claim 1, wherein the water-insoluble pigment (A) is at least one selected from the group consisting of organic pigments, vat dyes and disperse dyes.
7. The water-insoluble dye (A) is phthalocyanine, anthraquinone, perylene, perinone, dioxazine, quinacridone, diketopyrrolopyrrole, indigo / thioindigo, quinophthalone, isoindolinone, metal complex The dye derivative according to claim 1, wherein the dye derivative is at least one selected from the group consisting of an insoluble azo dye and a high molecular weight azo dye.
8. The compound (C) residue has a substituent, and the substituent is any one selected from the following group of hydrophilic groups, a group of lipophilic groups, and a group of reactive groups. A pigment derivative.
   A group of hydrophilic groups;
   Any anionic group selected from a carboxyl group, a sulfonic acid group, a phosphate ester group and a sulfate ester group;
   Of these anionic groups, alkali metal salts, ammonium salts, (mono, di, tri) alkylamine salts, (mono, di, tri) alkanolamine salts, (mono, di, tri)-(polyoxyalkylene) oxy A salt of any anionic group selected from alkylamine salts;
   Any cationic group selected from a tertiary amino group and a quaternary ammonium group;
   A salt of any one of these cationic groups selected from a halogenate, a sulfonate, and an alkylcarboxylate;
   Any nonionic group selected from a polyalcohol group and a polyethylene glycol group;
   Group of lipophilic groups;
   Any group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, and a halogen group;
   A group of reactive groups;
   Any group selected from the group consisting of a glycidyl group, a methylol group, and an alkoxymethyl group having 1 to 4 carbon atoms.
9. A liquid medium comprising a dye derivative according to any one of claims 1 to 8 as a colorant and an organic solvent, water or water-hydrophilic organic solvent mixed solvent as a dilution medium, or a polymerization medium A colorant comprising at least one of a polymerizable liquid medium comprising a polymerizable oligomer or a polymerizable monomer, or a resin medium comprising a synthetic resin.
10. The colorant according to claim 9, further comprising a polymer system dispersant or a low molecular weight dispersion aid as a dispersion aid.
11. For dyeing agent, printing agent, paint, printing ink, stationery, paint, resin colorant, electrophotographic printing developer, electrostatic printing developer or color filter pixel forming ink The colorant according to claim 9, which is any one.
12. 12. When coloring by a coloring method selected from dyeing, textile printing, painting, printing, writing, drawing, resin coloring, electrophotographic printing, electrostatic printing, or a color filter pixel forming method, A method for coloring an article, comprising using the colorant described in 1.
13. The color filter substrate according to any one of claims 9 to 11, wherein the color filter substrate is colored by a coloring method for forming pixels by any one of a photoresist method, an ink jet printing method, a printing method, a transfer method, and a pasting method. A method for coloring an article comprising using a colorant.