TWI511954B - Asymmetric polyazo pigments, methods for their manufacture, colorants and coloring methods - Google Patents

Description

Asymmetric polyazo pigment, manufacturing method thereof, coloring agent and coloring method

The present invention relates to an asymmetric polyazo dye, a method for producing the same, a coloring agent, and a coloring method. More specifically, the asymmetric polyazo dye is an asymmetric polyazo dye having two or more structural monoazo dye residues in one molecule, and a method for producing such an asymmetric type. , its coloring agent and its coloring method.

Conventionally, when a coloring is applied to an article by using a pigment, in order to adjust the desired color tone, a method of adjusting the color while selecting a pigment of an appropriate color while considering the desired performance, that is, performing the adjustment, is performed. color. Specifically, for the purpose of blending, a high-concentration processed product of a powder pigment or a pigment is appropriately selected, and coloring is performed by a method of mixing these. In this case, the pigment mixture may have different pigment physical properties such as the density of each pigment, the hardness of the coarse particles, and the particle size distribution, and may have different dispersibility and preservation stability in the preparation of the liquid pigment dispersion. Sexual differences. In this case, it can be solved by integrating a plurality of pigments to be mixed, and integration is achieved according to the following method. For example, mixing a plurality of pigments to be used, and dissolving in a solvent which can be dissolved together without causing decomposition and change of the pigment molecules, generally referred to as eutectoid or co-precipitation, or further A method of forming an integrated mixed crystal form according to molecular level is formed. Since the common solvent usable at this time is only such as sulfuric acid, the above method is mainly used for classification into polycyclic pigments such as phthalocyanine, lanthanide, quinacridone, peperone, and lanthanide. ,two A pigment such as a solid molecular structure.

In addition, the azo-based pigments are produced by mixing one or a plurality of kinds of diazo components, one type or a plurality of types of coupling components, or sequentially providing a coupling reaction, and mixing the types and uses of the pigments. Various coupling methods are used. For example, for a diazonium component or an even component, a plurality of components that undergo a coupling reaction with each other are generally referred to as a "mixed couple" method, or in a special case, a small amount is used for crystallinity and particle growth prevention. Mixed with ionic or nonionic diazo components or even components, generally referred to as "auxiliary coupling" method.

However, even if such a work is done, since the constituent pigments belong to individual molecules, it is only a mixture of pigment particles at best, and even if mixed crystals are applied, it is impossible to avoid a mixture of pigment molecules. Therefore, it is expected to develop a pigment having a structure of two or more chromophoric molecules in one molecule.

If the pigment obtained by the auxiliary coupling method using the above ionic component is an effective additive for crystal transfer and inhibition of crystal growth, it is expected to develop a pigment having a sulfonic acid group, a tertiary amino group or the like in the structure. Derivatives, as well as pigment derivatives that enhance the dispersibility of dispersed color pigments, reduce viscosity, enhance dispersion stability, and preserve stability.

As described above, the conventional pigments have improved pigmentation properties such as hue adjustment, crystallinity, and microparticle stability, depending on the coloring, co-precipitation, or mixed crystal form of the plural pigments, but it is inevitable that the pigments are individual. Defects caused by a mixture of pigment molecules. Therefore, development of a novel pigment coloring system that achieves pigment physical properties such as new hue, new crystallinity, and particle properties can be expected by using a dye having a different chromonic molecular structure in the same molecule. In addition, it is expected that by using an ionic diazo component or an even component, it is possible to reduce the viscosity and enhance the stability and the like in order to obtain an additive for crystal transfer and growth inhibition of a pigment or a solvent-based pigment dispersion type. Development of ionic derivatives of novel pigments.

Accordingly, it is an object of the present invention to provide the novel pigment coloring system described above, as well as ionic derivatives of novel pigments.

Conventionally, a pigment having a plurality of chromophores in the same molecule is a pigment of an azo-based high fast pigment and a high molecular weight azo pigment or a "polyazo pigment" (diazo pigment). For example, representative pigments are, for example, CI Pigment Red (hereinafter referred to as "PR") 144, PR166, PR221, PR214, PR242 belonging to a red pigment, CI Pigment Orange (hereinafter referred to as "PO") belonging to an orange pigment, 31, belonging to a brown pigment. CI Pigment Brown (hereinafter referred to as "PBr") 23 and the like. The synthesis methods of these polyazo pigments are condensation and coupling. When the synthesis is carried out by a condensation method, a carboxylic acid of a monoazo dye is formed by first coupling a diazo component to a hydroxynaphthoic acid, and then alanine bond is bonded by an aromatic diamine to form a polybut. A method of synthesizing a nitrogen pigment (diazo pigment).

The inventors of the present invention have intensively studied in order to achieve the object of the present invention, and have found that a molecular structure in which two identical azo dye residues are retained in the same molecule of the above polyazo pigment is further developed by using mutually different The azo pigment having two or more different chromonic molecular structures in the same molecule can be synthesized by using a diazo component or an even component, and the above problem can be solved by using a pigment having such a molecular structure, and the present invention has been completed.

That is, the asymmetric polyazo pigments provided by the present invention are mutually different monoazo dye residues (A) and monoazo pigment residues (B), and the use of exoaryl poly(carboamide) a) an asymmetric polyazo dye to be bonded, wherein each monoazo dye residue is obtained by coupling a coupling agent residue and a diazo component, and is selected from the following (1) to (3) The asymmetric polyazo dye molecular structure in the group formed.

(1) The respective coupler residues of the monoazo dye residue (A) and the monoazo dye residue (B) are the same as the residue of the coupling agent (C), and the diazo component is composed of different diazo components. (E) Molecular structure of a plurality of azo dyes coupled with a diazo component (F).

(2) Residues of coupling agent (C) and coupling agent (D) having different coupling agent residues of monoazo dye residue (A) and monoazo pigment residue (B), and diazo component A polyazo dye molecule structure coupled by the same diazo component (E).

(3) Residues of coupling agent (C) and coupling agent (D) having different coupling agent residues of monoazo dye residue (A) and monoazo pigment residue (B), and diazo component A polyazo dye molecular structure coupled by a different diazo component (E) and a diazo component (F).

The preferred embodiment of the above asymmetric polyazo dye of the present invention is as follows.

The coupling agent used to form the residue of the above coupling agent (C) or coupling agent (D) has a carboxyl group selected from the group consisting of: 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid , 2-hydroxy-3-indolecarboxylic acid, 2-hydroxy-3-dibenzofurancarboxylic acid, 2-hydroxy-1-indazolecarboxylic acid, and 2-hydroxy-11H-benzo[a]-carbazole a coupling agent of the same or different in the group consisting of 3-carboxylic acids; the above-mentioned exoaryl poly(carboniumamine) group having no or having a substituent selected from the group consisting of: phenylenediamine, diaminonaphthalene, Diaminobiphenyl, bis(aminophenyl)ether, methylene-bis(aminophenyl), bis(aminophenyl) sulfide, bis(aminophenyl)sulfonyl, and a residue of an aryldiamine in a group consisting of aminopyridines; the above-mentioned aryldiamines having one to two or more substituents derived from: alkane (carbon number: 1 to 10) Base, alkoxy (carbon number: 1-10), trifluoromethyl, halo; alkyloxycarbonyl, alkylsulfonyl, sulfonyl, alkyl sulfoamide , phenylsulfonyldiamine, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, alkylamine carbonyl, Anilinecarbonyl; carboxyl, sulfonate, sulfate, phosphate; amine, alkylimido, hydroxyalkylimino, dialkylamino, bis(hydroxyalkyl)amine, and quaternary Any one of the groups consisting of the alkylammonium groups is selected, or two or more groups which are the same or different from the group are selected.

The above diazo component (E) or diazo component (F) has no or a substituent, and has a skeleton derived from an allylamine molecule or a skeleton derived from a heterocyclic amine molecule; the above allylamine or The heterocyclic amine group has never had or has a substituent, and is selected from the group consisting of aniline, naphthylamine, aminoguanidine, aminoguanidine, aminodibenzofuran, and aminocarbazole; When the above substituent has a substituent, it is derived from: alkane (carbon number: 1 to 10) group, alkoxy group (carbon number: 1 to 10) group, trifluoromethyl group, halogen group, nitro group; Carbonyl, alkylsulfonyl, sulfonyl, alkylsulfonyldiamine, phenylsulfonyldiamine, alkylaminesulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, Alkylamine carbonyl, aniline carbonyl; carboxyl group, sulfonic acid group, sulfate group, phosphate group; amine group, alkyl imino group, hydroxyalkyl imino group, dialkylamino group, bis(hydroxyalkyl group) Any one of the group consisting of an amine group and a tetraalkylammonium group is selected, or two or more groups which are the same or different from the group are selected.

Furthermore, another embodiment of the present invention provides a method for producing the asymmetric polyazo dye, which is any of the following methods (1) to (3).

(1) [1] The carboxyl group of the coupling agent (C) is reacted with a nitroallylamine to form a "coupling agent nitro group" having a coupling agent for a nitro group, [2] the nitro group Reduction to form a "coupling amine substrate", [3] coupling of a monoazo dye carboxylic acid or an acid halide derivative to which a nitrogen component (E) is added to the coupling agent (C) a condensation reaction between the coupling amine substrate obtained in the above [2] to form a "pigment coupling agent" having a coupling agent of a monoazo dye, and [4] a dye coupling agent and a diazo component (F) a method of coupling to obtain an asymmetric polyazo dye having the same coupling agent (C) residue and different residues of the diazo component (E) and the diazo component (F);

(2) [1] The carboxyl group of the coupling agent (C) is reacted with a nitroallylamine to form a "coupling agent nitro group" having a coupling agent for a nitro group, and [2] the nitro group is reduced. The "coupling agent amine matrix" is formed, and [3] the carboxyl group or the mercapto halogen derivative of the separately prepared coupling agent (D) is subjected to a condensation reaction to form an "asymmetric coupling agent dimer", [4] The coupling agent residue of the dimer is coupled with the diazo component (E), thereby preparing residues having different coupling agents (C) and coupling agents (D) and the same diazo component. a method of asymmetric polyazo dyes of residues of (E);

(3) [1] The carboxyl group of the coupling agent (C) is reacted with a nitroallylamine to form a "coupling agent nitro group" having a coupling agent for a nitro group, [2] the nitro group Reducing to form a "coupling amine substrate", [3] coupling a "monoazo dye carboxylic acid or a fluorenyl halide derivative" containing a nitrogen-concentrating component (F) to the coupling agent (D) [2] The "coupling amine substrate" obtained is subjected to a condensation reaction to form a "pigment coupling agent" having a coupling agent of a monoazo dye, and [4] coupling the dye coupling agent to the diazo component (E). Thus, asymmetric polyazo dyes having different coupling agent (C) and coupling agent (D) residues, and different diazonium components (E) and diazo components (F) residues are obtained. The method.

Further, the coloring agent provided by the present invention is a coloring material containing the above asymmetric polyazo dye. The coloring agent may further contain any one of a liquid medium, a polymerizable liquid medium or a resin medium, and/or a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and One or more types of coating film forming materials are selected from the group consisting of crosslinking agents.

The coloring agent may be any one as long as the coloring material contains the asymmetric polyazo dye of the present invention, and may further contain a known pigment; the diluent medium may contain: an organic solvent system, an aqueous system or a water-hydrophilic organic solvent. Any one of a liquid medium composed of a solvent and a polymerizable liquid medium composed of a polymerizable oligomer or a polymerizable monomer; or a resin medium composed of a plasticizer, an oligomer, or a synthetic resin, and Or the coating film forming material contains one or more materials selected from the group consisting of a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent; Further, it further contains additives such as a polymerization system dispersant, a low molecular dispersant, a curing catalyst, and a polymerization catalyst.

Further, the coloring agent provided by the present invention is a coloring material containing the asymmetric polyazo dye, wherein the pigment is composed of a hydrophobic diazo component (E) and has an anionic or cationic property. The ionic group-containing diazo component (F) is composed of a coupled ionic pigment derivative, and has an asymmetric polyazo dye having the molecular structure of the asymmetric polyazo dye of the above (1) or (3); Further, the dispersing aid contains a compound having a cationic or anionic group having a ionic property to the above diazo component (F) and having a counter ion; and the diluted medium contains an organic solvent.

The coloring agent is preferably a coloring agent, a printing agent, a coating, a printing ink, a stationery, a painting tool, a resin coloring agent, an ink for inkjet printing, a developer for electronic photo printing, a developer for electrostatic printing, or a color. Any of the filter pixel forming inks.

Further, the coloring agent provided by the present invention contains an asymmetric type in which a hydrophobic diazo component (E) and a diazo component (F) having an anionic or cationic ionic group are coupled. The polyazo dye and the pigment; and the dispersing aid contains a dispersing agent of a polymerization system having a cationic or anionic group which is ionic with an asymmetric polyazo pigment; and a dilute medium is an organic solvent.

Furthermore, the coloring method of the article provided by the present invention uses the above coloring agent, and is used for: dyeing, printing, painting, printing, taking notes, drawing, resin coloring, inkjet printing, electronic photo printing, electrostatic column In the printing or color filter pixel forming method, any coloring method is selected and coloring is performed. Further, in the method for coloring the article according to the present invention, the color filter pixel forming method is formed on a color filter substrate by a photoresist method, an inkjet printing method, a printing method, a transfer method, or Pixel formation is performed by any method such as a pasting method. Moreover, the colored articles provided by the present invention are colored by these methods.

In the case where the pigment is used in the present invention, the pigment is selected from the group consisting of an anthraquinone pigment, a quinacridone pigment, a dioxopyrrolopyrrole pigment, a ruthenium thioate pigment, a pepertone pigment, and an anthracene. Pigments, phthalocyanine pigments, porphyrin pigments, isoporphyrin pigments, isoindolinone pigments, An organic pigment composed of a pigment, a quinacridone pigment, a nickel azo pigment, a metal complex pigment, an insoluble azo pigment, a soluble azo pigment, a high molecular weight azo pigment, and a carbon black pigment, composite In the group consisting of an inorganic pigment composed of an oxide pigment, an iron oxide pigment, and a titanium oxide pigment, at least one pigment or a mixture of two or more pigments or a mixed crystal pigment is selected; and the pigment is preferably a CI pigment. Red (hereinafter referred to as "PR") 5, PR9, PR122, PR123, PR146, PR166, PR168, PR171, PR177, PR216, PR224, PR226, PR242, PR254, CI Pigment Yellow (hereinafter referred to as "PY") 20, PY24, PY62, PY74, PY93, PY109, PY110, PY113, PY114, PY117, PY125, PY138, PY139, PY150, PY154, PY155, PY180, PY185, CI Pigment Blue (hereinafter referred to as "PB") 15:3, PB15:6, At least one of PB60, CI Pigment Green (hereinafter referred to as "PG") 7, PG36, PG58, poly(12-16) copper bromide phthalocyanine, CI Pigment Violet (hereinafter referred to as "PV") 19, and PV23 is selected.

According to the invention having the above constitution, it is possible to provide a novel dye of an asymmetric polyazo dye in which a different monoazo dye component is bonded in one molecule. Therefore, in the conventional pigment, the hue adjustment, the crystallinity, the microparticle stability, and the like can be achieved by using the coloring, coprecipitation, or mixed crystal form of different plural pigments, and the same in-molecular modification is used. A novel pigment having a different chromonic molecular structure can achieve novel pigments such as new hue, new crystallinity, and particulate matter, and a coloring method suitable for various uses of the pigment can be expected.

Further, by synthesizing a non-object azo dye in which an ionic group is introduced into one monoazo component, and then treating it with other pigments, it is effective as an additive for pigment crystal transfer and inhibition of crystal growth. A pigment derivative may be used as a pigment derivative in which the dispersibility of the solvent-based pigment-dispersed color pigment is improved, the viscosity of the dispersion is lowered, and the dispersion stability and long-term storage stability are improved.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.

The molecular structure of the asymmetric polyazo dye which imparts the features of the present invention is composed of different asymmetric molecular structures, and different monoazo dye residues (A) (in the following general formula) "AzA") and a monoazo dye residue (B) (hereinafter referred to as "AzB" in the general formula) are the following general formula (I) which is bonded to an exoaryl group by a carboamine group. The asymmetric polyazo dye shown. Further, "Ar" in the following formula (I) is an extended aryl skeleton of an extended aryldiamine described later, and -CONH-Ar-NHCO- is hereinafter referred to as "extended arylpoly(carboguanamine) group".

[AzA]-CONH-Ar-NHCO-[AzB] (I)

The asymmetric polyazo dye is obtained by the combination of the coupling agent component constituting the monoazo dye and the diazo component, and the following asymmetric molecular structures (1) to (3) can be obtained. Further, in the following general formula, the residue of the coupling agent (C) is referred to as "CpC", the residue of the coupling agent (D) is referred to as "CpD", and the residue of the diazo component (E) is referred to as "DzE". The residue of the diazo component (F) is referred to as "DzF".

(1) The respective coupling agent residues of the monoazo pigment residue (A) and the monoazo pigment residue (B) are the residues of the same coupling agent (C), and the diazo component is composed of different diazo The component (E) and the diazo component (F) are coupled to a polyazo dye molecular structure represented by the following general formula (II).

[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC]-N=N-[DzF] (II)

(2) respective coupler residues of the monoazo dye residue (A) and the monoazo dye residue (B), which are different coupling agents (C) and residues (C) of the coupling agent (D), [CpD], and the diazo component is a polyazo dye molecular structure represented by the following general formula (III) which is coupled by the same diazo component (E).

[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzE] (III)

(3) Residues of coupling agent (C) and coupling agent (D) having different coupling agent residues of monoazo dye residue (A) and monoazo pigment residue (B), and diazo component A polyazo dye molecule structure in which a different diazo component (E) and a diazo component (F) are coupled.

[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzF] (IV)

Next, a component constituting the above asymmetric polyazo dye and a method for synthesizing the same will be described.

The coupling agent (C) or (D) used for the formation of the residue is known to have a coupling position constituting the coupling component. Specifically, for example, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 2-hydroxy-3-indolecarboxylic acid, 2-hydroxy-3-dibenzofurancarboxylic acid, 2-hydroxyl group can be used. -1-carbazolecarboxylic acid or 2-hydroxy-11H-benzo[a]-carbazole-3-carboxylic acid having a carboxyl group. The carboxylic acid group of the coupling agent is reacted with a polyamine such as a aryl diamine described later, and the coupling agent residue is bonded to the exoaryl skeleton based on the carbon amide. Further, the coupling agent (C) or (D) is the case where the same coupling agent (C) is used and the different coupling agents (C) and (D) are used as described in the above (1) to (3).

Further, in the above-mentioned coupling agents (C) and (D) and a reaction with a polyamine, a carboxylamine-based polyamine is formed by reacting with a carboxyl group of a coupling agent (hereinafter collectively referred to as "extension aryl" The amine ") can be, for example, the following. For example: aromatic diamines from: phenylenediamine, diaminonaphthalene, benzidine, bis(aminophenyl)ether, methylene-bis(aminophenyl), bis(aminophenyl) A diamine selected from the group consisting of thioether, bis(aminophenyl)sulfonyl, diaminopyridine, and the like. Further, when the diamine has a substituent, the substituent is derived from an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, and a cyanogen group. At least one of the groups formed by the base or the like is selected. Further, when two or more substituent groups are used, a diamine to which the same or different substituents are introduced may also be used.

Hereinafter, examples of the molecular structure of the above asymmetric polyazo dye and the synthesis methods of the above are exemplified.

(1) A method for synthesizing an asymmetric polyazo dye having the same coupling residue [CpC] as the above general formula (II) but having a diazo component as a different component of (E) and (F), There is a method consisting of the following steps.

[1] A carboxylic acid (hereinafter referred to as "coupling carboxylic acid") of a coupling agent (C) (the residue is [CpC]) is reacted with a nitroallylamine to form a coupling agent having a nitro group. (hereinafter referred to as "coupling agent nitro group").

[CpC]-COX+NH ₂ -Ar-NO ₂ →[CpC]-CONH-Ar-NO ₂

(In the present invention, "X" means a halogen residue of a mercapto halide.)

[2] The nitro group is reduced, and the "coupler nitro group" is formed into a "coupling amine substrate".

[CpC]-CONH-Ar-NO ₂ →[CpC]-CONH-Ar-NH ₂

[3] Further, a "monoazo dye carboxylic acid" in which a coupling agent (C) (the residue is [CpC]) and a diazo component E (a portion where [DzE] is formed after the reaction) is prepared ( Hereinafter, the case of "pigment carboxylic acid" is abbreviated as follows.

[DzE]-N ₂ X+[CpC]-COOH→[DzE]-N=N-[CpC]-COOH

[4] A "monoazo dye carboxylic acid" is used as a mercapto halogen derivative and is subjected to a condensation reaction with the above "coupling amine substrate" to form a coupling agent having a monoazo dye ("pigment coupling agent") .

[DzE]-N=N-[CpC]-COX+[CpC]-CONH-Ar-NH ₂ →[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC]

[5] The dye coupling agent is coupled to the diazo component F (the portion which becomes [DzF] after the reaction).

[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC]+[DzF]-N ₂ X→[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC ]-N=N-[DzF]

Hereinafter, an outline of the reaction mechanism of the above general formula (II) will be given.

(2) The method for synthesizing the asymmetric polyazo dye having the same coupling agent component and the same diazo component as shown in the above general formula (III), and having the following steps.

[1] a "coupling amine base" of the above coupling agent (C) (the residue of which is [CpC]), and a mercapto halogen derivative of a coupling agent (D) (the residue of which is [CpD]) carboxylic acid The condensation reaction is carried out to form an "asymmetric coupler dimer".

[CpC]-CONH-Ar-NH ₂ +[CpD]-COX→[CpC]-CONH-Ar-NHCO-[CpD]

[2] The coupler residues of the two are coupled to the diazo component E (the portion where DzE is formed after the reaction).

[CpC]-CONH-Ar-NHCO-[CpD]+2[DzE]-N ₂ X→[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[ DzE]

Hereinafter, an outline of the reaction mechanism of the above general formula (III) will be given.

(3) The method for synthesizing an asymmetric polyazo dye having a different coupling agent component and diazo component as shown in the above general formula (IV) is as follows.

[1] A "monoazo dye carboxylic acid" in which a coupling agent (D) (the residue is [CpD]) and a diazo component (F) (a portion where [DzF] is formed after the reaction) is prepared.

[DzF]-N ₂ X+[CpD]-COOH→[DzF]-N=N-[CpD]-COOH

[2] The coupling agent (C) (the residue is [CpC]) of the "coupling amine substrate" and the "monoazo pigment carboxylic acid" fluorenyl halide derivative are condensed to form a "pigmentation couple" mixture".

[DzF]-N=N-[CpD]-COX+[CpC]-CONH-Ar-NH ₂ →[DzF]-N=N-[CpD]-CONH-Ar-NHCO-[CpC]

[3] The "pigment coupling agent" is coupled to the diazo component E (the portion where DzE is formed after the reaction).

[DzF]-N=N-[CpD]-CONH-Ar-NHCO-[CpC]+[DzE]-N ₂ X→[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD ]-N=N-[DzF]

And other manufacturing methods.

Hereinafter, an outline of the reaction mechanism of the above general formula (IV) will be given.

In the synthesis of the above-mentioned "coupling agent carbonyl (nitro)allyl decylamine" which is a coupling agent nitro group, the nitroallylamine used may, for example, be 4-nitrated aniline or 2-chloro-4-nitrification. Aniline, 2,5-dichloro-4-nitrated aniline, 2-methyl-4-nitrated aniline, 2-methoxy-4-nitrated aniline, 2,5-dimethoxy-4-nitrated aniline, 2 ,5-diethoxy-4-nitrated aniline, 2,6-dimethoxy-4-nitrated aniline, 2-cyano-4-nitrated aniline, 6-chloro-2-cyano-4-nitrated aniline , 4-amino-5-bromo-3-cyano-nitrified benzene, 2-nitrated 1-naphthylamine, 4-nitrated 1-naphthylamine, 2-amino-5-nitrated diphenyl ketone, 4 -Amino-4'-nitrated-diphenyl sulfide, 2-amino-5-nitrated pyridine, and the like.

The nitro group of the above-mentioned "coupling carbonyl (nitro) allyl decylamine" is reduced to form a "coupling agent carbonyl (amino) allyl decylamine", and then reacted to form an asymmetric polybut. Nitrogen pigment. The aryldiamine residue of the dicarbamide which forms the polyazo pigment corresponds to the above nitroallylamines, for example, p-phenylenediamine, 2-chloro-1,4-benzobenzene Amine, 2,5-dichloro-1,4-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2 -methoxy-1,4-phenylenediamine, 2,5-dimethoxy-1,4-phenylenediamine, 2,5-diethoxy-1,4-phenylenediamine, 2-Chloro-1,4-phenylenediamine, 2-chloro-5-methyl-1,4-phenylenediamine, 2,6-dichloro-1,4-phenylenediamine, 2-cyano Base-1,4-phenylenediamine, 6-chloro-2-cyano-1,4-phenylenediamine, 5-bromo-3-cyano-1,4-phenylenediamine, 1,4 -diaminonaphthalene, 1,2-diaminonaphthalene, 2,5-diamino-diphenyl ketone, bis(4-aminophenyl) sulfide, 2,5-diaminopyridine, 3 , 4-diaminopyridine and the like.

The diazo component constituting the above polyazo dye will be described. The diazo component E (the portion where the [DzE] is formed after the reaction) and the diazo component F (the portion where the [DzF] is formed after the reaction) are a conventionally known diazo component, and the molecular skeleton may have, for example, The following constructor. For example, an aromatic amine or a heterocyclic amine selected from the group consisting of aniline, naphthylamine, aminoguanidine, aminoguanidine, aminodibenzofuran, aminocarbazole, etc., and these may also have Substituents exemplified below. For example, the nonionic substituent is, for example, an alkane (carbon number: 1 to 10) group, an alkoxy group (carbon number: 1 to 10) group, a trifluoromethyl group, a halogen group, a nitro group; an alkylsulfonyl group; Aminesulfonyl, alkylsulfonyldiamine, phenylsulfonyldiamine, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, aniline carbonyl, etc.; The base system is, for example, a carboxyl group, a sulfonic acid group, a sulfate group, a phosphate group, etc.; and the cationic substituent is, for example, an amine group, an alkylimino group, a hydroxyalkylimino group, a dialkylamino group, A bis(hydroxyalkyl)amino group, a quaternary alkanolammonium group or the like. The use of an allylamine or a heterocyclic amine which selectively introduces one or two or more identical or different substituents is also shown by the method for synthesizing the above asymmetric polyazo dye, and the same is used. The situation with the use of different people.

A hydrophobic diazo component which does not have an ionic group is a conventionally known diazo component. For example: aniline, toluidine (o-, m- or p-), 2,4-dimethylaniline, 3,4-dimethylaniline, 2-methoxy-5-methylaniline (para cresidine), A Oxyaniline (o-, m- or p-), aminophenol (o-, m- or p-), nitroaniline (o-, m- or p-), chlorinated aniline (o-, m -or p-), 2,5-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, 2-chloro-4-nitrated aniline, 5 -Chloro-2-nitrated aniline, 2,6-dichloro-4-nitrated aniline, o-fluoroaniline, 2,4-difluoroaniline, m-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline , 2-aminothiophenol, 2-amino-5-nitrated benzonitrile, 2-amino-3-bromo-5-nitrated benzonitrile, diphenylamine, 1-naphthylamine, 2-naphthylamine , 3-amino-9-ethylcarbazole, 2-aminothiazole, 2-amino-5-nitrazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole , 1-aminoindole, 2-aminoindole, o-(phenylsulfonyl)aniline, 2-ethylsulfonyl-5-trifluoromethylaniline, 4-benzylsulfonyl-neo Methoxyaniline, o-methoxyaniline-4-sulfonyldiethylguanamine, o-methoxyaniline-4-sulfoethyl, 6-benzoguanamine-m--4-methylphenylamine, 4,4 -dichloro-2-amino group Diphenyl ether, 4-benzoguanamine-2,5-dimethoxyaniline, 9-aminoacridine, 6-aminocarbazole, and the like. In the present invention, an asymmetric polyazo dye which is coupled to only such a hydrophobic diazo component having no ionic group is referred to as an "asymmetric polyazo pigment".

Further, examples of the diazo component having an ionic group include o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 2-chloroaniline-3-sulfonic acid, and 4-chloro. Aniline-2-sulfonic acid, 4-chloroaniline-3-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2-nitrated aniline-4-sulfonic acid, o-methoxyaniline-5-sulfonic acid , p-Methoxyaniline-5-sulfonic acid, o-toluidine-4-sulfonic acid, m-toluidine-4-sulfonic acid, p-toluidine-2-sulfonic acid, 2-chloro-p-toluidine-3-sulfonate Acid, 2-chloro-p-toluidine-5-sulfonic acid, 4-chloro-m-toluidine-2-sulfonic acid, 3-amino-6-chlorotoluene-4-sulfonic acid, 3-amino-6- Chloro-4-sulfobenzoic acid, 1-amino-8-naphthalenesulfonic acid, 2-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 5-amino-1-naphthalene Sulfonic acid, 6-amino-1-naphthalenesulfonic acid, 5-amino-3-naphthalenesulfonic acid, 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid, 1-amino-2- Hydroxy-4-naphthalenesulfonic acid, 6-amino-4-hydroxy-2-naphthalenesulfonic acid, 7-amino-4-hydroxy-2-naphthalenesulfonic acid, 1-amino-2-indolesulfonic acid, 1-amino-5-anthracenesulfonic acid, 1-amino-8-anthracenesulfonic acid, aminoxycarbazolesulfonic acid, 9-aminoacridinium sulfonic acid, o-amine benzoic acid, p-aminobenzoic acid Wait.

Further, when an ionic group-containing diazo component is used, the ionic group of the asymmetric polyazo dye obtained may be a salt form. For example, when the ionic group is a sulfonic acid group, the alkali system to be a counter ion may, for example, be an alkali metal hydroxide such as lithium, sodium or potassium; or a polyvalent metal such as calcium, aluminum, zinc, magnesium, nickel or iron. Hydroxide; ammonia; (mono, di- or tri)alkyl (C ₁ ~ C ₂₀ ) amines, alkanol (C ₁ ~ C ₁₀ ) amines, and alkyl (C ₁ ~ C ₂₀ ) ammonium chloride Wait. In the present invention, these asymmetric polyazo dyes having an ionic group are referred to as "ionic pigment derivatives".

The above asymmetric polyazo pigments can be used in the same manner as conventionally known pigments, such as dyeing, printing, painting, printing, writing, drawing, resin coloring, ink jet printing. , electronic photo printing, electrostatic printing, or color filter pixel forming methods.

These coloring agents can be used in various known applications, and can be used as conventionally known dyes, printing agents, paints, printing inks, stationery, painting tools, resin colorants, inks for inkjet printing, and developers for electronic photo printing. A developer for electrostatic discharge or an ink for color filter pixel formation.

Further, the ionic pigment derivative using the above-described diazo component having an ionic group is not limited to the above-described color materials for various uses, and the following can be used. For example, when the pigment is crystallized or micronized, or in organic materials such as paints, printing inks, solvent-based or ultraviolet-curable inkjet inks, color filter inks, or thermosetting acrylic inks. When a pigment is used for a solvent dispersion coloring agent or a coloring agent for plastics, a pigment to be additionally used may be added for the purpose of suppressing crystal transfer, suppressing crystal growth, improving dispersibility, and improving heat resistance. In particular, when the pigmented pigment derivative is subjected to a pigmentation treatment (pigmentation treatment), it is effective in addition to a pigment crude material (crude pigment) or a coarse particle pigment, and in a liquid pigment dispersion type color, The use of pigments in combination with ionic pigment derivatives can also result in excellent dispersion performance and improved storage stability. When such a pigment crystal growth inhibitor and a dispersion stabilizer are used, the ionic pigment derivative is preferably insoluble in an organic solvent medium, and is introduced into about one or less of the pigment component of the pigment derivative. The average number of good families is 0.5~0.1. Further, an organic solvent-based coloring agent such as a paint or a gravure ink, or a color filter pixel-forming photoresist ink may be used in addition to a pigment, a film forming material, and a diluent medium, and the ionic pigment derivative may have the opposite As the ionic group-containing polymer, a dispersant which is a pigment is used.

The colorant-based pigment of the present invention preferably contains the asymmetric polyazo dye of the present invention described above. Depending on the application, it is preferable to contain an asymmetric polyazo pigment in particular, and further contain a known pigment as needed, and a diluent medium is used, for example, an organic solvent system, a water-based or water-hydrophilic organic solvent mixed solvent system. a liquid medium; a polymerizable oligomer; a polymerizable liquid medium composed of a polymerizable monomer; a plasticizer, an oligomer, a resin medium composed of a synthetic resin, and/or a coating film forming material containing: One or more materials selected from the group consisting of a thermoplastic polymer, a reactive polymer, a reactive oligomer, a polymerizable monomer, and a crosslinking agent, and further containing a polymerization system dispersant and a low molecular dispersion as needed The coloring agent prepared by the agent, the curing catalyst, the polymerization catalyst, and the like.

Further, when preparing a coloring agent comprising the above asymmetric polyazo pigment, a high-concentration pigment processed product in which a high concentration of a pigment to be used is finely dispersed in a dispersion medium is prepared in advance, and a coloring agent can be obtained by using the same. The manufacturing tends to be easy. The liquid high-concentration pigment dispersion is called "primary color" or "base ink", and the high-concentration pigment dispersion for plastic coloring is called "masterbatch" or "master powder" (below). There is a case where these are collectively referred to as "base color"). Preferably, the primary colors are in the asymmetric polyazo dye, and further, if necessary, further containing a necessary pigment, and the medium is preferably a suitably known liquid medium, a polymerizable liquid medium or a resin medium containing a coloring agent, as needed. Further, a polymerization system dispersant or a low molecular dispersant used as a dispersing aid is further used.

In the resin-based dispersing agent which disperses the pigment in the present invention, a known resin-based dispersing agent which is conventionally used in a coloring agent can be used arbitrarily, and is not particularly limited. Further, the dispersion medium is a suitable solvent or an aqueous medium. Further, the coloring agent of the present invention may be appropriately added using conventionally known additives such as a dispersing aid, a smoothing agent, an adhesion agent, and the like.

As a resin binder for a coating film forming material (when it is called "carrier" or "varnish" depending on the application), a room temperature drying type or baking varnish type resin binder and a photosensitive resin binder are used. The room temperature drying type or baking varnish type resin bonding agent is, for example, a resin binder used for image recording materials such as printing dyes, paints or printing inks, stationery, ink jet printing, electronic photo printing, and electrostatic printing. On the other hand, the photosensitive resin binder is a photosensitive resin binder used for various coating materials such as ultraviolet curability or electron beam curing, a coating agent, a printing ink, an inkjet ink, and the like.

Specific examples of the room temperature-drying type or the varnish-type resin binder include a synthetic rubber resin, an acrylic resin, a styrene-based (co)polymer, and a polyvinyl butyral resin; a polyester resin; an amine; Base resin modified polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamine resin, soluble polyimide resin, soluble polyamidoximine Resin, soluble polyester bismuth amide resin, alkyd resin, amino alkyd resin, epoxy resin, chlorinated rubber resin, enamel resin, fluororesin, cellulose acetate resin, nitrocellulose resin a water-soluble salt of a hydroxyethyl cellulose, a styrene-maleate copolymer, a water-soluble salt of a (meth)acrylate-based (co)polymer, a water-soluble amino alkyd resin, The water-soluble amino-based polyester resin and the water-soluble polyamine-based resin may be used alone or in combination of two or more.

The film forming material may further contain a reactive group or may not be contained. The reactive group is, for example, a methylol group, an alkylhydroxymethyl group, an isocyanate group, a masking isocyanate group, an epoxy group or the like. Further, depending on the use, an oligomer or a monomer may be used, and a crosslinking agent such as a methylol melamine-based, isocyanate-based or epoxy-based crosslinking agent may be further used in combination.

Specific examples of the energy ray-curable coating film forming material such as an ultraviolet curable resin or an electron beam curable resin are, for example, a photosensitive cyclized rubber resin, a photosensitive phenol resin, or a photosensitive polyacrylate resin. Resin, photosensitive polyamine resin, photosensitive polyimide resin, etc.; and unsaturated polyester resin, polyester acrylate resin, poly epoxy acrylate resin, polyurethane acrylate A binder such as a resin, a polyether acrylate resin, or a polyol acrylate resin; or a binder which is a monomer for a reactive diluent is further added thereto.

The coloring agent of the present invention is used for forming a color filter pixel, and a suitable coloring agent is used in the forming method thereof, and a known color filter substrate, a printing method, a transfer method is used on the color filter substrate. Forming a pixel by a method such as a paste method. A coloring composition for image display such as a color filter for a liquid crystal display or an advertisement for display, such as a glass substrate or a plastic plate substrate.

The asymmetric polyazo dye of the present invention can also be used as a coloring agent for plastics. The colored plastics are known as thermoplastic plastics and thermosetting plastics. Examples of the thermoplastic plastics include polyolefins such as polyethylene, ethylene copolymer, and polypropylene; polystyrene, ABS, AS, styrene copolymer, vinyl chloride resin, methacrylic resin, polycarbonate, and polyfluorene. Amine, polyacetal, thermoplastic polyester, cellulose-based plastic, phenyl ether resin, fluororesin, thermoplastic elastomer, and the like. Further, examples of the thermosetting plastics include unsaturated polyester resins, epoxy resins, enamel resins, polyurethane resins, melamine resins, and phenol resins. In the coloring agent for plastics, as described above, the asymmetric polyazo dye used or the pigment used in combination is prepared in advance to be finely dispersed in a high concentration in a dispersion medium to form a high concentration pigment microdispersion. It is used as a "masterbatch", which makes it easier to manufacture colorants.

[Examples]

Next, the present invention will be described in more detail with reference to specific production examples and examples. Also, the "parts" and "%" in the text are quality benchmarks unless otherwise stated.

[Synthesis Example 1: Synthesis of "Coupling Amine Matrix"] (a) Synthesis of "coupler nitro group"

According to the usual method, in 188.1 parts (1.0 mol) of 3-hydroxy-2-naphthoic acid (hereinafter referred to as "BONA"), 138.1 parts (1.0 mol) of 4-nitrated aniline was suspended in toluene, and trichlorination was dropped. Phosphorus, and is subjected to countercurrent boiling. Then, water is injected, and alkali is formed by using sodium carbonate, and toluene is subjected to steam distillation. Then, it is filtered, washed with water, and dried. The obtained product was added to methanol, neutralized with sodium hydroxide, dissolved, and filtered to be insoluble, and then acetic acid was added thereto to precipitate. The precipitate was filtered, washed with methanol, washed with water, and dried to obtain 283.6 parts of 3-hydroxy-4'-nitrated-2-naphthylamine. The yield was 92%. Hereinafter, the coupling agent having a nitro group is referred to as "coupling agent nitro-1".

Similarly, the carboxylic acid (hereinafter referred to as "coupling carboxylic acid") of the coupling agent described in the first column of Table 1 was condensed with the nitroallylamine described in the second column to obtain column 3, respectively. The "coupling agent nitro group" described in the position.

(b) Synthesis of "coupling amine matrix"

In 4,000 ml of methanol, 308.2 parts (1.0 mol) of the "coupler nitro-1" obtained in the above (a) was charged, and sodium hydroxide was added thereto, and after dissolution, concentrated hydrochloric acid was dropped to precipitate and disperse. Subtle. According to the usual method of iron powder reduction, 344 parts of reduced iron was added, concentrated hydrochloric acid was dropped, stirred for 10 hours, and refluxed to carry out reduction. After cooling to normal temperature, concentrated hydrochloric acid was added dropwise and stirred for 30 minutes. The product was filtered, and washed with methanol to obtain a methanol paste of an amine base hydrochloride. Next, the container was charged with 8,500 ml of methanol, and the paste of the amine base hydrochloride obtained above was charged while stirring, sodium hydroxide was added thereto, and after dissolved, concentrated hydrochloric acid was added to carry out acid precipitation and filtration. . The paste of the above amine base hydrochloride was dispersed in the liquid of the container, and neutralized with 28% aqueous ammonia to adjust the pH to 9.0 to 9.5 to obtain 3-hydroxy-4'-amino-2-naphthylamine benzene. 256.0 parts. The yield was 92%. Hereinafter, the coupling agent having an amine group obtained is referred to as "coupling agent amine base-1".

Similarly, the "coupling agent nitro group" described in the first column of Table 2 obtained in the above (a) was subjected to reduction to obtain a "coupling amine substrate" described in the second column.

[Synthesis Example 2: Synthesis of "Pigment Carboxylic Acid"] (a) Diazotization of 2,5-dichloroaniline

According to a conventional method, 260 ml of water and 32.41 parts (0.20 mol) of 2,5-dichloroaniline were added together in a diazotization reactor, and an acidic suspension was formed using 74.7 parts of concentrated hydrochloric acid. Under cooling, 15.2 parts (0.22 mol) of sodium nitrite was added to carry out a diazotization reaction. It was confirmed that the diazotization reaction was completed, the excess sodium nitrite was decomposed, and the insoluble matter was filtered to prepare a diazo liquid of 2,5-dichloroaniline.

(b) Synthesis of "pigment carboxylic acid"

According to the usual method, 2,000 ml of water was placed in the coupling reaction apparatus, and BONA (37.62 parts, 0.20 mol) was added. After cooling to 5 ° C or lower, the diazo liquid of 2,5-dichloroaniline obtained in the above (a) was slowly injected, and the pH was adjusted to 7.0 to 7.5 with a 10% aqueous sodium hydroxide solution to carry out a coupling reaction. The end of the coupling reaction was confirmed, filtered, washed with water, and dried to obtain 68.6 parts of a carboxylic acid of an azo dye. The yield was 95%. Hereinafter, the carboxylic acid (4-((2,5-dichlorophenyl)-azo)-3-hydroxy-2-naphthoic acid) of the obtained azo dye is referred to as "coloring matter-1".

Similarly, the "coupling carboxylic acid" described in the first column of Table 3 was coupled with the diazo component described in the second column to obtain the "pigment carboxylic acid" described in the third column.

Further, the above "HBCA" means 2-hydroxy-11H-benzo[a]carbazole-3-carboxylic acid.

[Synthesis Example 3: Synthesis of "Pigment Coupler"]

In the same manner as in the synthesis example 1 (a), 2,000 ml of chlorobenzene was charged into the reaction apparatus, and then 72.23 parts (0.20 mol) of "coloring acid-1" obtained in Synthesis Example 2 (b) was charged. And 55.65 parts (0.20 mol) of "coupling amine base-1" obtained in Synthesis Example 1 (b), and phosphorus trichloride was added dropwise. Then, the temperature was raised to 110 ° C, and the mixture was stirred for 8 hours to carry out a condensation reaction. Cool to room temperature, filter, and wash with chlorinated benzene and methanol. Next, the obtained reaction product was added to 4,000 ml of methanol, dissolved with sodium hydroxide, and the insoluble portion was filtered. Then, acid was added to precipitate, and the mixture was filtered, washed with methanol and water, and dried to obtain 94.5 parts of an azo dye-bonded coupling agent. The yield was 76%. Hereinafter, the obtained azo dye bond coupling agent is referred to as "pigment coupling agent-1".

Similarly, the "pigment carboxylic acid" described in the first column of Table 4 was condensed with the "coupler amine substrate" described in the second column to obtain the "pigment coupling agent" described in the third column.

[Synthesis Example 4: Synthesis of "Asymmetric Coupler Dimer"]

In the same manner as in Synthesis Example 3, 2,000 ml of chlorobenzene was charged into the reaction apparatus, followed by charging 55.46 parts of 2-hydroxy-11H-benzo[a]carbazole-3-carboxylic acid (HBCA) (0.2 mol). The ear) and 55.65 parts (0.20 mol) of the "coupling amine substrate-1" obtained in Synthesis Example 1 (b) were dropped with phosphorus trichloride, and the mixture was heated to 110 ° C and stirred for 8 hours to carry out a condensation reaction. Cool to room temperature, filter, and wash with chlorinated benzene and methanol. Further, it was dissolved in alkali methanol, precipitated by adding an acid, washed with methanol and water, and dried to obtain 96.8 parts of a dimer having different coupling agents. The yield is 90%. Hereinafter, the obtained heterocoupler dimer is referred to as "asymmetric coupler dimer-1".

[Synthesis Example 5: Synthesis of "Asymmetric Polyazo Pigment"] (a) Diazotization of 2-chloroaniline

A diazotization reaction of 12.76 parts (0.10 mole) of 2-chloroaniline was carried out in a diazotization reactor according to a usual method. It was confirmed that the diazotization reaction was completed, and the excess sodium nitrite was decomposed by the amine sulfonic acid, and filtered to obtain a diazo liquid of 2-chloroaniline.

(b) Synthesis of "asymmetric polyazo pigments"

In the coupling reaction apparatus, 1,400 ml of nitrobenzene and 62.14 parts (0.10 mol) of "Pigment Coupler-1" obtained in Synthesis Example 2 were charged, and the mixture was cooled to 5 ° C or less, and the above addition was carried out according to the above (a). The diazo liquid of 2-chloroaniline obtained was subjected to a coupling reaction. It was confirmed that the coupling reaction was completed, and it was filtered, washed with water, and dried to obtain 72.2 parts of a double nitrogen pigment having a different diazo component. The yield was 95% and the hue was red. Hereinafter, the obtained double nitrogen pigment is referred to as "asymmetric polyazo pigment-1".

Similarly, the "pigment coupling agent" described in the first column of Table 5 and the diazo component described in the second column were subjected to diazotization, and a coupling reaction was carried out to obtain "non-" as described in the third column. Symmetrical polyazo pigments."

[Synthesis Example 6: Synthesis of "Asymmetric Pigment Derivative"] (a) Diazotization of Aminobenzenesulfonic Acid

According to a conventional method, a diazotization reaction of 17.32 parts (0.10 mole) of aminobenzenesulfonic acid was carried out in a diazotization reactor. It was confirmed that the diazotization reaction was completed, and the excess sodium nitrite was decomposed by the amine sulfonic acid, and filtered to obtain a diazo liquid of p-aminobenzenesulfonic acid.

(b) Synthesis of "asymmetric pigment derivatives"

According to the usual method, 4,600 ml of methanol and 66.7 parts (0.10 mol) of "pigment coupling agent-6" were charged into the coupling reaction apparatus, and the mixture was cooled to 5 to 10 ° C, and the amine obtained by the above (a) was slowly added. The diazo solution of benzenesulfonic acid is subjected to a coupling reaction. It was confirmed that the coupling reaction was completed, acidity was formed by dilute hydrochloric acid, and the mixture was filtered, washed with water, and dried to obtain 81.9 parts of an asymmetric double nitrogen pigment derivative having a sulfonic acid group on a unilateral azo dye residue. The yield was 96% and the hue was red. Hereinafter, the asymmetric double nitrogen dye derivative having a sulfonic acid group on one side is referred to as "asymmetric pigment derivative-1".

Similarly, the "pigment coupling agent" described in the first column of Table 6 was coupled with the diazo component described in the second column to obtain the "asymmetric dye derivative" described in the third column.

Hereinafter, the names of the chemical substances of the "asymmetric polyazo pigment" obtained in the above examples are exemplified.

(1) Asymmetric polyazo pigment-1

N,N'-(1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-((2,5- Dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(2) Asymmetric polyazo pigment-2

N,N'-(1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-((2-chloro- 5-trifluoromethylphenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(3) Asymmetric polyazo pigment-3

N,N'-(2-chloro-1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-(( 2,5-dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(4) Asymmetric polyazo pigment-4

N,N'-(2,5-Dichloro-1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4' -((2,5-dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(5) Asymmetric polyazo pigment-5

N,N'-(2-methyl-1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-( (2,5-dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(6) Asymmetric polyazo pigment-6

N,N'-(2-methyl-1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-( (2-chloro-5-trifluoromethylphenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(7) Asymmetric polyazo pigment-7

N,N'-(1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbiniumamine-1'-((4-nitrobenzene) Azo)-2'-hydroxy-11'H-benzo[a]carbazole-3'-carboguanamine

(8) Asymmetric polyazo pigment-8

N,N'-(1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbiniumamine-1'-((2-chlorobenzene) Azo)-2'-hydroxy-11'H-benzo[a]carbazole-3'-carboguanamine)

(9) Asymmetric pigment derivative-1

N,N'-(2-methyl-1,4-phenylene)-4-((4-sulfophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'- ((2-chloro-5-trifluoromethylphenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

(10) Asymmetric pigment derivative-2

N,N'-(1,4-phenylene)-4-((4-sulfophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-((2,5 -dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbinium)

[Example 1: Baking paint for metal products]

5 parts of "asymmetric polyazo pigment-1" obtained in Synthesis Example 5, and ethyl acetate of a reactive acrylic styrene resin composed of an alkyl methacrylate-styrene copolymer having a hydroxyl group and a carboxyl group 45 parts of solution (solid content: 50%), glass beads were added according to a usual method and dispersed using a paint shaker. Next, 5 parts of methoxymethyl melamine crosslinking agent (solid content: 50%), 0.1 part of anti-separator, and 44.9 parts of xylene were added, and further dispersed to prepare red styrene acrylate for metal products. coating. The obtained paint is sprayed on the metal product, and the paint is applied, and the metal product is subjected to a beautiful red paint. Moreover, by using aluminum powder to form an acrylic paint for metal products, it is possible to perform a beautiful red paint with excellent weather resistance.

[Example 2: Printing paste for woven fabric]

An aqueous pigment dispersion liquid was obtained by using 25 parts of "asymmetric polyazo pigment-2" obtained in Synthesis Example 5, 10 parts of a nonionic pigment dispersant, 1 part of an antifoaming agent, and 64 parts of water. Next, 25 parts of reactive acrylic alkyl ester latex (solid content 40%), 0.5 part of antifoaming agent, 1 part of dispersing agent, 3 parts of oil-drop type emulsion dispersion stabilizer, 38 parts of turpentine oil, and water 12.5 In the portion, 20 parts of the aqueous pigment dispersion obtained above was used to obtain a paste-like red paste in which an azo pigment was dispersed. Then, in the obtained red paste, an epoxy-based crosslinking agent was used in an amount of 1% to prepare a red printing paste. The red printing paste was printed on a polyester-cotton blend fabric by squeegee printing, and hardened at 120 ° C for 15 minutes to obtain a red printed matter.

[Example 3: Polyurethane coating agent]

A white methyl ethyl ketone dispersion (solid content: 30%) of a polyether polyol diphenylmethane diisocyanate polyurethane having a carboxyl group, 100 parts, and a polyether polyol diphenylmethane diisocyanate polyuric acid 5 parts of an ester methyl ethyl ketone solution (solid content: 50%) and 2.5 parts of a polycarbodiimide crosslinking agent (solid content: 20%) were thoroughly mixed. 1 part of an asymmetric polyazo pigment paste which was mixed with 0.5 parts of "asymmetric polyazo pigment-3" obtained in Synthesis Example 5 and 1.0 part of an adipate-based plasticizer was added thereto, and thoroughly mixed. The red polyurethane coating solution is prepared. This was coated on the surface of the polyester woven fabric to about 200 g/m ² and dried to obtain a red fiber processed product.

[Example 4: aqueous intaglio ink]

15 parts of "asymmetric polyazo pigment-4" obtained in Synthesis Example 5, a carboxyl group-containing polyurethane resin obtained from a polycarbonate polyol and an aliphatic isocyanate (solid content: 30%) 60 5 parts of water-dispersible wax (solid content: 30%), 1 part of antifoaming agent, 5 parts of polycarbodiimide cross-linking agent (solid content: 50%), and 14 parts of water are blended and prepared. A red water-based gravure ink is obtained.

Similarly, PB15:3 (phthalocyanine blue pigment), PY74 (monoazo yellow pigment), and PBK7 (carbon black pigment) were used to prepare a blue, yellow, and ink aqueous intaglio ink containing the same. The obtained 4-color printing ink is printed on a transparent colorless plastic film such as polyethylene, polypropylene, polyester or nylon. Get a beautiful printed film.

[Example 5: Resin molding]

5 parts of "asymmetric polyazo pigment-5" obtained in Synthesis Example 5, 20 parts of titanium oxide white pigment, and 75 parts of polyethylene resin powder used as a pigment dispersant, and a Hansu mixer (powder high speed) The mixer was mixed to obtain a powder colorant (dry color). Next, 1.0 part of the obtained powder coloring agent was blended into 100 parts of polybutylene terephthalate (PBT) resin pellets, mixed by a Hansui mixer, and red resin pellets were formed by an extruder. The obtained red particles were molded by an in-line screw injection molding machine to obtain a red PBT resin molded plate excellent in pigment dispersibility.

[Example 6: Transparent resin formed plate]

2 parts of an acrylic resin (polymethyl methacrylate) red masterbatch containing 20% of "asymmetric polyazo pigment-6" obtained in Synthesis Example 5, and blended into 100 parts of acrylic resin particles, using Han Su The mixer was mixed, and the extruder was used to form red resin particles. The obtained red particles were molded by an inline screw type injection molding machine to obtain a red transparent acrylic resin molded plate excellent in pigment dispersibility.

The same change was made to an acrylic resin, and the polycarbonate resin pellets were colored with polycarbonate resin red masterbatch pellets, and molded to obtain a red transparent polycarbonate molded panel excellent in pigment dispersibility.

[Example 7: Raw liquid coloring spinning]

50 parts of "asymmetric polyazo pigment-7" obtained in Synthesis Example 5 and 50 parts of ethyl bis-stearate powder used as a pigment dispersant were mixed with a Han Su blender to obtain a pigment. Divided into 50% dry color. Next, 1.0 part of the obtained dry color material was blended into 99.0 parts of polypropylene resin pellets, mixed by a Hansui mixer, and kneaded by a squeeze type 40 m/m extruder to form 0.5% red resin pellets. The obtained red resin pellets were spun by a melt spinning machine to obtain a bright red polypropylene stock solution colored yarn excellent in pigment dispersibility of denier 10 denier.

[Example 8: Digital electronic printing] (1) (Modulation of resin composition containing a high concentration of pigment)

30 parts of "asymmetric polyazo pigment-4" obtained in Synthesis Example 5 as a red pigment, and a polyester resin of bisphenol A-bis(propylene glycol ether) and terephthalic acid (average molecular weight: about 15,000) 70 parts, which were kneaded by a twin roll machine to complete a polyester masterbatch prepared with a red pigment. Further, a polyester master batch of a black pigment was prepared in the same manner as described above except that "asymmetric polyazo pigment-8" obtained in Synthesis Example 5 was used instead of black pigment. Further, a blue and yellow polyester master batch was obtained in the same manner as described above except that PB15:3 using a blue pigment and PY74 using a yellow pigment were used.

(2) Modulation of coloring composition for image recording, and printing of full-color electronic photographs

Then, according to the formulation (parts) of the following Table 7, the polyester masterbatch of each color obtained above, the above-mentioned polyester resin, and the chromium salt-based negative charge control agent are kneaded according to the usual method, and then cooled and then subjected to coarsening. After being crushed, fine pulverization was carried out by a jet mill, and a fine powder of a coloring composition for image recording of 5 to 7 μm was obtained by a classifier. The colloidal ceria is added with a fluidizing agent and mixed with the magnetic iron powder of the carrier to form an electrophotographic dry developer of indigo, magenta, yellow and black. Printed with an electronic photo-based full-color laser printer to obtain bright, full-color electronic photo prints.

[Example 9: Formation of color filter pixels] (1) (Modulation of pigment dispersion for color filters) (modulation of red pigment dispersion)

20 parts of "Asymmetric Polyazo Pigment-2", 2 parts of "Asymmetric Pigment Derivative-1", benzyl methacrylate-methacrylic acid-(2-hydroxyethyl) methacrylate copolymer (Morby: 60:20:20, weight average molecular weight 30000) (hereinafter referred to as "BzMA-MAc-HEMA copolymer") 15 parts, cationic polymerization system dispersant 4 parts, and PGMA (59 parts), using continuous The horizontal medium disperser was dispersed to obtain a red pigment dispersion (hereinafter referred to as "red pigment dispersion-1").

Same as (1) above, but instead of asymmetric polyazo pigment-2, PR254 (dioxopyrrolopyrrole red pigment) is used instead, and "Asymmetric Pigment Derivative-1" is replaced by "Non" The symmetric dye derivative-2" was dispersed to obtain a red pigment dispersion (hereinafter referred to as "red pigment dispersion-2").

(Modulation of pigment dispersions of green, blue, yellow and purple)

Same as (1) above, but instead of asymmetric polyazo pigment-2, used instead of PG36 (copper phthalocyanine green pigment), PB15:6 (ε-type copper phthalocyanine blue pigment), PY150 (nickel mismatch) Yellow pigment), and PV23 (two In the purple pigment, a pigment composition having a known sulfonic acid group-containing pigment derivative was added, and a pigment dispersion liquid having a pigment content of 20% was obtained in the same manner as in the above (1). Hereinafter, "green pigment dispersion-1", "blue pigment dispersion-1", "yellow pigment dispersion-1", and "purple pigment dispersion-1" are respectively referred to.

(2) (modulation of photosensitive photoresist ink of each pigment)

In order to form red (R), green (G), and blue (B) pixels on the glass substrate of the color filter, two colors of the red pigment dispersion prepared according to the above (1), and green, blue, and A yellow and purple pigment dispersion was obtained according to the formulation (parts) of Table 8 below to obtain a photosensitive red photoresist ink, a photosensitive green photoresist ink, and a photosensitive blue photoresist ink.

In the above, TMPTA means trimethylolpropane triacrylate; HEMPA means 2-hydroxyethyl-2-methylpropan-1-one; and DEAP means 2,2-diethoxyacetophenone.

(3) (RGB pixel formation of color filter)

The glass substrate was mounted on a spin coater, and the photosensitive red photoresist ink was first subjected to spin coating at 300 rpm for 5 seconds, and then spin coating was performed at 1,200 rpm for 5 seconds. Subsequently, pre-baking was carried out for 10 minutes at 80 ° C, and a mask having a mosaic pattern was placed on the coated surface of the glass substrate, and exposure was performed using an ultra-high pressure mercury lamp at a light amount of 100 mJ/cm ² using a proximity exposure machine. Next, development and washing are performed by a dedicated developer and special cleaning to form a red mosaic pattern on the glass substrate.

Next, using the photosensitive green photoresist ink and the photosensitive blue photoresist ink shown in Table 8, the coating and baking varnish were applied according to the above method to form a green mosaic pattern and a blue mosaic pattern, and RGB color filter was obtained. sheet.

The obtained color filter has excellent spectral curve characteristics, is excellent in light fastness and heat resistance, and has excellent light penetration properties, and is excellent as a color filter for liquid crystal color display. nature.

(industrial availability)

According to the above invention, a novel dye of an asymmetric polyazo dye in which a different monoazo dye component is bonded to each other in one molecule will be provided. Therefore, in the conventional pigment, the hue adjustment, the crystallinity, the microparticle stability, and the like can be achieved by using the coloring, coprecipitation, or mixed crystal form of different plural pigments, and the same in-molecular modification is used. A novel pigment system having a different chromonic molecular structure can be expected to have a novel pigment system that achieves pigment physical properties such as new hue, new crystallinity, and particle properties.

In addition, by performing a pigment treatment on an symmetrical azo dye (pigment derivative) in which an ionic group is introduced into a single-sided monoazo component, it is effective as a pigment modifier for pigment crystal transfer and crystal growth control. It is also suitable for use as a performance improving agent such as an organic solvent-based pigment-dispersed color pigment having improved dispersibility, a viscosity reduction of a dispersion, dispersion stability, and long-term storage stability.

Claims (8)

An asymmetric polyazo dye having a different monoazo dye residue (A) and a monoazo dye residue (B) linked by an exoaryl poly(carboamide) group, Here, each monoazo dye residue is obtained by coupling a coupling agent residue and a hydrophobic diazo component, and has an asymmetric polyazo pigment selected from the group consisting of the following (1) to (3). Molecular structure: (1) The residue of each coupling agent in the monoazo dye residue (A) and the monoazo pigment residue (B) is the same as the residue of the coupling agent (C), and the hydrophobic diazo component is A polyazo dye molecular structure represented by the following general formula (II) by a different hydrophobic diazonium component (E) and a hydrophobic diazonium component (F) [DzE]-N=N-[CpC]- CONH-Ar-NHCO-[CpC]-N=N-[DzF](II); (2) coupler residues in the monoazo dye residue (A) and the monoazo dye residue (B) a different coupling agent (C) and a residue of the coupling agent (D), and the hydrophobic diazonium component is a polyazo which is represented by the following general formula (III) by coupling the same hydrophobic diazonium component (E) Pigment molecular structure [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzE](III); (3) Single couple a coupling agent (C) and a coupling agent (D) residue which are different from each of the coupling agent residues in the nitrogen pigment residue (A) and the monoazo pigment residue (B), and the hydrophobic diazo component is The molecular structure of the polyazo dye represented by the following general formula (IV) by coupling different hydrophobic diazo components (E) with the hydrophobic diazo component (F) [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzF](IV); here, CpC is the residue of the coupling agent (C), and CpD is an even a residue of the mixture (D), DzE is a residue of the hydrophobic diazo component (E), DzF is a residue of the hydrophobic diazo component (F), and Ar represents an extended aryl skeleton of the extended aryldiamine; The coupling agent used to form the residue of the coupling agent (C) or the coupling agent (D) has a carboxyl group, and the coupling agent is selected from 3-hydroxy-2-naphthoic acid and 6-hydroxy-2-naphthoic acid, respectively. 2-hydroxy-3-indolecarboxylic acid, 2-hydroxy-3-dibenzofurancarboxylic acid, 2-hydroxy-1-oxazolecarboxylic acid and 2-hydroxy-11H-benzo[a]-carbazole-3 - the same or different coupling agents in the group consisting of carboxylic acids; the above-mentioned aryl poly(carbon oxime) group having no or having a substituent selected from the group consisting of phenylenediamine, diaminonaphthalene, and diamine Biphenyl, bis(aminophenyl)ether, methylene-bis(aminophenyl), bis(aminophenyl) sulfide, bis(aminophenyl)sulfonyl and diaminopyridine Residues of the aryldiamines constituting the group The above hydrophobic diazonium component is selected from the group consisting of aniline, toluidine (o-, m- or p-), 2,4-dimethylaniline, 3,4-di Toluidine, 2-methoxy -5-methylaniline (para cresidine), methoxyaniline (o-, m- or p-), aminophenol (o-, m- or p-), nitroaniline (o-, m- or P-), aniline chloride (o-, m- or p-), 2,5-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloro Aniline, 2-chloro-4-nitrated aniline, 5-chloro-2-nitrated aniline, 2,6-dichloro-4-nitrated aniline, o-fluoroaniline, 2,4-difluoroaniline, m-trifluoromethylaniline , 2-chloro-5-trifluoromethylaniline, 2-aminothiophenol, 2-amino-5-nitrated benzonitrile, 2-amino-3-bromo-5- Nitrobenzonitrile, diphenylamine, 1-naphthylamine, 2-naphthylamine, 3-amino-9-ethylcarbazole, 2-aminothiazole, 2-amino-5-nitrazole, 2- Aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 1-aminoindole, 2-aminoindole, o-(phenylsulfonyl)aniline, 2-ethylsulfonium 5--5-trifluoromethylaniline, 4-benzylsulfonyl-o-methoxyaniline, o-methoxyaniline-4-sulfonyldiethylguanamine, o-methoxyaniline-4-sulfoethyl , 6-benzoguanamine-m--4-toluidine, 4,4-dichloro-2-aminodiphenyl ether, 4-benzoguanamine-2,5-dimethoxyaniline, 9- A group consisting of amino acridine, 6-aminocarbazole, and the like. The asymmetric polyazo dye according to claim 1, wherein the above-mentioned extended aryldiamine has one to two or more substituents derived from an alkane (carbon number: 1 to 10). Base, alkoxy (carbon number: 1-10), trifluoromethyl, halo; alkyloxycarbonyl, alkylsulfonyl, sulfonyl, alkyl sulfoamide, Phenylsulfonium diamine, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, alkylamine carbonyl, aniline carbonyl; carboxyl, sulfonate, sulfate, phosphate Any one selected from the group consisting of an amine group, an alkyl imino group, a hydroxyalkyl imino group, a dialkylamino group, a bis(hydroxyalkyl)amino group, and a quaternary alkanolammonium group, or Two or more bases of the same or different are selected in the group. A method for producing an asymmetric polyazo dye, which is an asymmetric polyazo dye of the first application of the patent application, which is one of the following methods (1) to (3): (1) [ 1] reacting the carboxyl group of the coupling agent (C) with the nitroallylamine In response, a coupling agent nitro group having a nitro coupling agent is formed, [2] the nitro group is reduced to form a "coupling agent amine matrix", and [3] a separately prepared coupling agent (C) is coupled. The "monoazo dye carboxylic acid or acid halide derivative" of the hydrophobic diazo component (E) is condensed with the "coupling amine substrate" obtained in the above [2] to form a a "pigment coupling agent" having a coupling agent of a monoazo dye, [4] coupling the dye coupling agent to the hydrophobic diazo component (F), thereby obtaining a residue having the same coupling agent (C), And a method of asymmetrical polyazo dyes having different hydrophobic diazo components (E) and residues of hydrophobic diazo components (F); (2) [1] a carboxyl group having a coupling agent (C) Reacting with nitroallylamine to form a "coupling agent nitro group" which is a coupling agent having a nitro group, [2] reducing the nitro group to form a "coupling agent amine matrix", [3] preparing separately The carboxyl group or the fluorenyl halide derivative of the coupling agent (D) is subjected to a condensation reaction to form an "asymmetric coupling agent dimer", [4] to make the dimer The coupling agent residues of the two are coupled with the hydrophobic diazonium component (E), thereby preparing residues having different coupling agents (C) and coupling agents (D), and the same hydrophobic diazonium component (E) a method of asymmetrical polyazo dyes of residues; (3) [1] reacting a carboxyl group possessed by the coupling agent (C) with a nitroallylamine to form a coupling agent having a nitro group "Coupling agent nitro group", [2] reducing the nitro group to form a "coupling agent amine matrix", [3] coupling the separately prepared coupling agent (D) to the hydrophobic diazo component (F) An azo dye carboxylic acid or a fluorenyl halide derivative, and the "coupler amine matrix" obtained in the above [2] The condensation reaction is carried out to form a "pigment coupling agent" which is a coupling agent having a monoazo dye, [4] coupling the dye coupling agent to the hydrophobic diazo component (E), thereby producing a different coupling. A method of mixing the residue of the coupling agent (C) with the coupling agent (D) and the asymmetric polyazo pigment of the hydrophobic diazo component (E) and the residue of the hydrophobic diazo component (F). A coloring agent comprising the asymmetric polyazo dye of any one of claims 1 to 3 as a color material. The coloring agent according to claim 4, further comprising any one of a liquid medium, a polymerizable liquid medium or a resin medium, and/or a thermoplastic polymer, a reactive polymer, and a reactivity One or more selected coating film forming materials selected from the group consisting of an oligomer, a polymerizable monomer, and a crosslinking agent. A method for coloring an article, which uses the coloring agent of the fourth application patent, according to dyeing, printing, painting, printing, taking notes, drawing, resin coloring, inkjet printing, electronic photo printing, electrostatic printing, Coloring is performed by any of the coloring methods selected in the color filter pixel forming method. The coloring method of the article of claim 6, wherein the color filter pixel forming method is on a color filter substrate, using a photoresist method, an inkjet printing method, a printing method, a transfer method, Or pixel formation by either method of the pasting method. A colored article is colored according to the coloring method of claim 7 of the patent application.