TW201139371A - Asymmetrical polyazo dye, manufacturing method for same, colouring agent and colouring method - Google Patents

Abstract

Disclosed is an asymmetrical polyazo dye obtained by linking a monoazo dye residue (A) and a different monoazo dye residue (B) via an allylene poly(carboxamide) group. The asymmetrical polyazo dye is characterized in that each monoazo dye residue is formed by coupling a coupler residue and a diazo component, and in that the asymmetrical polyazo dye has a specific asymmetrical polyazo dye molecular structure.

Description

201139371 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION 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 above-mentioned asymmetric polyazo dye system - octagonal + + asymmetric azo dye having two or more structural monoazo dye residues, and a method for producing such an asymmetric type , its coloring agent and its coloring method. [Prior Art] Conventionally, when a coloring is applied to an article by using a pigment, in order to adjust to a desired color tone, a pigment of a selected color tone is selected in consideration of a desired property, and the color is adjusted while viewing the color tone. The method of implementing color grading. Specifically, the blending of the finely processed products of the powder pigment or the pigment is appropriately selected and the square yarns to be mixed are appropriately colored. In this case, the simple pigment mixture 'has a phenomenon such as the density of each pigment, the hardness of the coarse particles, the particle size distribution, and the like, and the dispersion of the liquid pigment dispersion may be different, and the stability may be preserved. Sexual differences. In this case, it is possible to use a combination of a plurality of pigments to be integrated and to solve the problem. For example, a plurality of pigments to be used for mixing are dissolved and dissolved in a solvent which can be dissolved together in a solvent which does not undergo decomposition and change of the pigment molecules, or is more advanced to form a basis. The molecular level is a method of forming a mixed crystal form. Since the commonality available at this time is only such as sulfuric acid, etc., the above method mainly uses the pigments of the enamel system, the bite system, and the like. In the case of polycyclic pigments, such as phthalocyanine, azolidinone, anthraquinone, and diterpene, etc., the azo-based pigment system adopts one or more kinds of diazo components. With i or a plurality of pairs. The component is divided into the ages, or a manufacturing method for performing the coupling reaction is sequentially provided. Various coupling methods are employed in accordance with the type of the pigment and the use. For example, for a type of heavy IU or coupling age, a component that causes a couple to react with it, a method of "mixed couple", or a special case, for crystallinity and particle growth. A small amount of a method of mixing ionic or nonionic diazonium sulphate. If the knife is formed into a knife or even into a knife, it is generally called "auxiliary coupling law" ..., and even if it is the same: L Fu, because the constituent pigments belong to individual molecules, it is only a mixture of particles at best, and even if it is implemented Mixed crystals, but still not expected to belong to the mixture of pigment molecules. Therefore, it is expected to develop a pigment having a structure of two or more chromophoric molecules in one molecule. 'The pigment obtained by the above-mentioned ionic component (4) auxiliaries is an effective additive for crystallizing the pigment and inhibiting the growth of the crystal. It is also expected to develop a pigment derivative having a hetero group, a tertiary amino group or the like in the structure. , and pigment derivatives that can improve the performance of dispersive color, such as touch, reduce the degree of dispersal, improve dispersion stability and preserve stability. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) 099145164 4 201139371 As described above, the conventional pigments can be used for coloring, co-precipitation, or mixed crystal forms of different plural pigments, and the hue adjustment is improved. Pigment properties such as day-to-day and fine particle stability are not avoided, and the defects caused by the composition of the pigments belonging to the individual pigment molecules are unavoidable. Therefore, it is possible to use a pigment having a structure of a different chromonic molecule in the same molecule, and to develop a coloring property such as a new hue, a new crystallinity, or a particle property, and to develop a color. Or the even-synthesis component, which is developed for the crystallization of pigments for pigment transfer and growth inhibition, or for the dispersion of ionic derivatives of new axial materials with low viscosity and improved stability. The object of the invention is to provide the above-mentioned new pigment coloring system and an ionic derivative of a novel pigment. (Means for Solving the Problem) It is known that a pigment having a plurality of chromophores in the same molecule uses an azo intercalation property. A pigment of a pigment' and a high molecular weight azo pigment or simply a "polyazo pigment" (bisazo pigment). For example, representative pigments are, for example, CI Pigment Red (hereinafter referred to as "pR") 144, pRl66, pR221, PR214, PR242 belonging to red pigment, cI Pigment Orange (hereinafter referred to as "P〇") belonging to orange pigment 31, belonging to brown The ci·pigment brown (hereinafter referred to as "PBr") 23 of the pigment. 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 hydroxynaphthoic acid, and then alanine bond is bonded by an aromatic diamine to form a plurality of The method of azo dye (diazo pigment) was carried out by the synthesis of 099145164 5 201139371. The inventors of the present invention have found that a good structure in which the same molecule of the above polyazo pigment retains two identical azo colorant residues is further developed in order to achieve the above object of the present invention, by making a difference The diazo component or the diastereous component can be combined with an azo pigment having two or more kinds of non-color molecular structures in the molecule, and the above problem can be solved by using a dye having such a molecular structure, and the present invention has been completed. That is, the asymmetric polyazo dyes provided by the present invention are mutually different monoazo dye residues (A) and monoazo pigment residues (8)' utilizing an extended aryl group (Carbamine) The amide))-based asymmetric polyazo dye, wherein each monoazo dye filament is coupled by a coupling-based group and a diazo component, and has a structure selected from the following (1) to (3) The molecular structure of the asymmetric polyazo dyes in the group is formed. (1) The respective coupling agent residues of the early azo & aldehyde residue (A) and the single thief pigment residue (B) (4) coupling agent (residue of Q, and the diazo component is composed of different diazonium components (E) The molecular structure of the azo dye that is coupled with the diazo component (7). (2) A coupling agent having a different coupling residue of the monoazo dye residue (A) and the monoazo pigment residue (B) ( C) a residue of the coupling agent (D), and the diazo component is a polyazo dye molecular structure coupled by the same diazo component (E). (3) Soap azo pigment residue (a) and mono even The respective coupling agent residues of the gas pigment residue (b) are different coupling agents (C) and residues of the coupling agent (D), and the heavy bismuth components are composed of different diazonium components (E) and diazo components ( F) coupling of multiple azo colors 099145164 6 201139371 Prime molecular structure. The preferred embodiment of the above asymmetric polyazo dye of the present invention is such that the following coupling agent (c) or coupling agent (D) is formed. The coupling agent used in the residue has a carboxyl group selected from the group consisting of: % hydroxy 2 - naphthoic acid, 6 · benzyl-2-naphthoic acid, 2 _ 3 蒽 蒽, _ 3 _ Dibenzo benzoic acid, 2 · thio- 1+ of the same or different coupling agents in the group consisting of the acid and the 2_ thiol_11H 々 and (5) octagonal winter tickic acid; the above aryl aryl (carbon amide) based system does not have or have The substituent is selected from the group consisting of phenylamine, diaminonaphthalene, diaminobiphenyl, bis(aminophenyl)ether, fluorenylene-bis(private phenyl), bis(aminophenyl) a residue of an aryldiamine in a group consisting of thiosazide, bis(aminophenyl) fluorenyl, and diaminopyridine; the above aryldiamine has one to two or more substitutions The substituent is derived from: 垸 (carbon number: 1 to 10) group, alkoxy (carbon number: 1 to 1 fluorene) group, trifluoromethyl group, halogen group, alkyl group, and base group. Base, amine aryl, alkyl sulfoamide, phenylsulfonamide, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, alkyl Amine carbonyl, aniline carbonyl; carboxyl group, sulfonic acid group, sulfate group, phosphate group; amine group, alkyl imino group, hydroxyalkyl imino group, dialkylamino group, bis(hydroxyalkyl)amino group And selecting a group from the group consisting of a quaternary alkylammonium group, or Two or more groups of the same or different groups are selected in the group. The above diazonium component (E) or diazo component (F) has no or has a substituent ' 099145164 7 201139371 and has a skeleton derived from an allylamine molecule. Or a skeleton derived from a heterocyclic amine molecule; the above allylamine or heterocyclic amine has never had or has a substituent ' and from: aniline, naphthylamine, aminoguanidine, aminoguanidine, aminodiphenyl Any one of the group consisting of furan and amine-based saliva; when the substituent has the substituent 'from: alkane (carbon number: 1 to 10), alkoxy (carbon number: 1 to 10) a group, a trifluoromethyl group, a fluorenyl group, a nitro group; an alkyloxycarbonyl group, an alkylsulfonyl group, an amine sulfonyl group, a succinyl diamine group, a phenylsulfonyl diamine group, an alkylamine sulfonate Sulfhydryl, aniline sulfonyl, amine carbonyl, benzoguanamine, alkylamine carbonyl, aniline carbonyl; carboxyl, sulfonate, sulfate, phosphate; amine, alkylimine, hydroxyalkane Selecting any one of the group consisting of a benzylidene group, a dialkylamino group, a bis(hydroxyalkyl)amino group, and a quaternary alkylammonium group, or selecting the same from the group or Different bases of 2 or more. 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] to separately prepare a "monoazo dye decanoic acid, or an acid halide derivative" that incorporates a nitrogen-concentrating component (E) on the coupling agent (C). "Condensation reaction with the "coupling amine substrate" obtained in the above [2]" to form a "pigment coupling agent" having a coupling agent of a monoazo dye [4] to make the dye coupling agent and the diazo component (F) Coupling, thereby making 099145164 8 201139371 an asymmetric polyazo dye having the same coupling agent (C) residue and different diazonium components (e) and diazonium component (F) residues (2) [1] The carboxyl group of the coupling agent (C) is reacted with a nitroallylamine to form a "coupling agent" having a coupling agent of a positive group, [2] The stone succinyl group is reduced to form a "coupling amine substrate", and [3] is subjected to a condensation reaction of a separately prepared coupling agent (D) having a ruthenium group or a fluorenyl hydrazine derivative. "#董子称^ coupling agent-monomer"[4] makes the coupler residue of the s-heomer, the diazo component (Ε) is coupled, thereby making different a method of coupling the coupling agent (c) with the residue of the coupling agent (D) and the asymmetric polyazo dye of the same diazonium component (E); (3) [1] coupling agent (C) The carboxyl group has a reaction with a nitroallylamine to form a "coupling agent matrix" having a coupling agent for a nitro group, and [2] a reduction of the nitro group to form a "coupling agent amine matrix", [3] The "monoazo dye carboxylic acid or fluorenyl halide derivative" in which the nitrogen component (ρ) is added to the coupling agent (D) is separately prepared and condensed with the "coupler amine substrate" obtained in the above [2]. The reaction forms a "pigment coupling agent" having a coupling agent of a monoazo dye, and [coupling the dye-coupled heavy nitrogen component (6), thereby producing a different coupling agent (C) and a coupling agent (9). A method of a residue and an asymmetric polyazo dye of a different residue of the diazo component (6) and the diazo component (F). Further, the coloring agent provided by the present invention is a coloring material containing the above asymmetric polyazo dye. The coloring agent may further comprise a liquid medium, a polymerizable liquid medium or a resin medium towel, a riding medium, and/or a thermoplastic, 099145164 9 201139371 polymer, a back-up polymer, a reactive filament, a polymerization. One or more types of coating film forming materials are selected from the group consisting of a monomer and a crosslinking agent. The coloring agent may contain a known pigment as long as the coloring material contains the asymmetric polyazo pigment of the present invention, and the diluent medium may contain an organic solvent system, a water system or a water/hydrophilic organic compound. Any one of a liquid medium composed of a solvent mixed solvent and a polymerizable liquid medium composed of a polymerizable oligomer or a polymerizable monomer; or a resin composed of a plasticizer, an oligomer, or a synthetic resin may be used. f, 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; It is also necessary to further improve additives containing a polymerization system dispersant, a low molecular dispersant, a hardening catalyst, a polymerization catalyst, and the like. Further, the coloring agent to be used in the present invention is a coloring material containing the asymmetric polyazo dye. The coloring matter is composed of a hydrophobic heavy gas component (E) and anionic or cationic. The ionic group-containing diazo component (F) is composed of a coupled ionic pigment derivative, and has the asymmetric polybrene dye molecule asymmetric asymmetric polyazo dye of the above (1) or (3); and 'dispersed The auxiliary agent 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 medium contains an organic solvent. The coloring agent is preferably a coloring agent, a printing agent, a coating, a printing ink, a stationery, a drawing utensil, a resin coloring agent, an ink for inkjet printing, an electronic photo column 099145164 201139371 printing developer, and a developer for electrostatic printing. Or a color filter like any of the inks. 'Used again' The coloring agent's coloring material provided by the present invention contains diazo which is made to have a hydrophobic weight & (E) and an anionic or ionic ion filament (F)' Coupling asymmetric polyazo dyes and pigments; and dispersing aids containing ionicity with asymmetrical polyazo dyes as counter-ionic cationic or anionic groups (four) complexes (four); Organic solvents. The method of coloring the articles provided by the present invention is to use the above-mentioned agents, such as: dyeing, printing, painting, printing, taking notes, tracing, tree-tanning, inkjet printing, electronic Coloring is performed by selecting any of the coloring methods in photo printing, electrostatic printing, or color light pixel forming methods. Further, in the method for coloring the above-mentioned article, the method for forming a color light-emitting sheet is formed on a color filter substrate by a photoresist method, an inkjet printing method, a printing method, a transfer method or a pasting method. In one method, pixel formation is performed: In addition, the colored articles provided by the present invention perform coloring by using these methods. s The present invention is the use of a pigment from: onion 酉 酉 颜料 pigment, bite _ series pigment, dioxo ^ 并 ^ 咯 咯 颜料 颜料 pigment, scatter · thio-based pigment, Pei Li (four) Pigments, $based pigments, phthalocyanine pigments, π(tetra)linescent pigments, 引木琳 pigments, isoindolinone pigments, akisaki cultivating pigments \ 啥 酮 酮 颜料 颜料 、 、 、 、 、 、 、 金属 金属 金属 金属 金属 金属 金属 金属099145164 11 201139371 machine pigment, carbon black pigment, composite oxide pigment, iron oxide pigment, titanium oxide pigment, etc., which are composed of a pigment, an insoluble azo pigment* azo pigment, and a high molecular weight azo pigment. In the group consisting of inorganic pigments, at least one pigment or a mixture of two or more pigments or a mixed crystal pigment is selected; the pigment is preferably (1. Pigment Red (hereinafter referred to as "卩! 1") 5, ?119, ?11122, ?11123, 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, PY 138, PY139, PY150, PY154, PY155, PY180, PY185, CI·Pigment Blue (hereinafter referred to as “pb”) 15 : 3, PB15 : 6, PB60, CI Pigment Green (hereinafter referred to as “pG”) 7, PG36, PG58 At least one of poly(12 to 16) copper bromide phthalocyanine, cI pigment violet (hereinafter referred to as "pv") 19, and PV23 is selected. (Effect of the invention) According to the present invention having the above configuration, one molecule can be provided. A novel dye of an asymmetric polyazo dye having different monoazo dye components, respectively, thereby obtaining a hue which can be achieved by using a color, co-precipitation, or mixed crystal form of a different plural pigment in a conventional pigment. Adjusting, and improving the physical properties of pigments such as crystallinity and micronization stability. By using (4) the same - a new amount of pigments with the same chromophoric molecular structure in the molecule, pigment properties such as new hue, new crystallinity, and particle properties can be achieved. The new sample 'can be expected to turn over (4) Yan _ each view of the color of the square coating. In addition, 'synthesis in the towel - monoazo component on the ionic group of non-target 099145164 12 201139371 azo pigment, and then When other pigments are treated, they form It is an effective pigment derivative for pigment crystal transfer and an additive for suppressing crystal growth, and it is also possible to use a solvent-based pigment-dispersed color pigment for improved dispersibility, viscosity reduction of dispersion, and dispersion stability and long-term storage stability. [Embodiment] The present invention will be described in more detail with reference to the preferred embodiments of 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 (Β) (hereinafter referred to as "ΑζΒ" in the general formula), which is 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 aryldiamine described later, and -CONH-Ar-NHCO- is referred to as "arylene-based poly(carboguanamine) group". [AzA]-CONH-Ar-NHCO-[AzB] (I) The above asymmetric polyazo dye is obtained by the combination of a coupling agent component constituting a monoazo pigment and a diazo component, and the following (1) can be obtained. (3) Asymmetric molecular structure. 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) Recombination of monoazo dye residue (A) and monoazo dye residue (B) 099145164 13 201139371 Reagent residue 'is the residue of the same coupling agent (c), and the diazo component is different The diazo component (E) and the diazo component (F) are coupled to a polydisplace dye molecular structure represented by the following general formula (11). [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC]-N=N-[DzF] (Π) (2) Monoazo pigment residue (A) and monoazo pigment residue Each of the coupling agent residues of the group (B) is a different coupling agent (Q and the residue of the coupling agent (D) [CpC], [CpD], and the diazo component is coupled by the same diazo component (E). The polyazo dye molecular structure shown in the following general formula (III) [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzE] (ΠΙ) ( 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 (ρ) [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpD]-N= N-[DzF] (IV) Next, a component constituting the asymmetric polyazo dye and a method for synthesizing the same will be described. A coupling agent (C) or (D) used for forming a residue is known. It is known to have a coupling position constituting an even component. Specifically, for example, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 2-hydroxy-3-indolecarboxylic acid, 2-hydroxy-3 can be used. -099145164 14 20113 9371 A benzoic acid, 2-hydroxy-1-oxazolinic acid, or 2-hydroxyl-11H-benzo[a]-carbazole-3-carboxylic acid, etc. having a carboxyl group. The carboxylic acid group is reacted with a polyamine such as a aryl diamine described later, and the coupling agent residue is based on a carbon amide bonded to an exoaryl skeleton. Further, the coupling agent (c) or (D) is used. As described in the above (1) to (3), there are cases where the same coupling agent (c) is used, and when different coupling agents (C) and (D) are used. Further, the coupling agent (C) shown above is used. And (D), in the reaction with a polyamine, a polyamine which reacts with the carboxyl group of a coupling agent to form a carboamine group (hereinafter referred to as "extended aryl diamine"), for example, the following. For example: Aromatic private amines from: phenylenediamine, diaminonaphthalene, benzidine, bis(aminophenyl)ether, methylene-bis(aminophenyl), bis(aminophenyl) sulfide a diamine selected from the group consisting of bis(aminophenyl) 1⁄2 fluorenyl, diaminopyridine, etc. Further, when the above diamine has a substituent, the substituent is derived from: alkane (carbon number: 1 to 10) base, burning oxygen (carbon number: KH)) The base group, the third group, the methyl group, the tooth group, the aryl group, and the like are selected from at least i. Further, when two or more substituent groups are used, a diamine which is introduced with the same or different substituents may also be used. Hereinafter, the molecular structure of the above asymmetric polyazo dye and examples of the synthesis methods thereof will be exemplified. The same, but the combination of heavy pigments (1) The above formula (II), the coupling agent residue [CpC] is a phase nitrogen component, and the asymmetric polyazo formation method of (E) and (F) are different components, There is a method consisting of the following steps. [1] A coupling agent (C) (the residue of which is [CpC]) (hereinafter referred to as "coupling agent 099145164 15 201139371 carboxylic acid") is reacted with a nitroallylamine to form a nitro group. Coupling agent (hereinafter referred to as "coupling agent nitro group"). [CpC]-COX+NH2-Ar-N〇2->[CpC]-CONH-Ar-N〇2 (In the present invention, "X" means a halogen residue of a mercapto halide.) [2] Reduction The nitro group forms a "coupling agent nitro group" to form a "coupling amine substrate". [CpC]-C0NH-Ar-N02->[CpC]-C0NH-Ar-NH2 [3] Further, the coupling agent (C) (the residue is [CpC]) is prepared, and the diazo component E (reaction) Then, the "monoazo dye carboxylic acid" (hereinafter referred to as "pigment carboxylic acid") which is coupled to the [DzE] portion is formed.

[DzE]-N2X+[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-mentioned "coupling amine substrate" to form a coupling agent having a monoazo dye ("pigment coupling agent") . [DzE]-N=N-[CpC]-COX+[CpC]-CONH-Ar-NH2 — [DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC] [5] The coupling agent is coupled with the diazo component F (the portion which becomes [DzF] after the reaction).

[DzE]-N=N-[CpC]-CONH-Ar-NHCO-[CpC]+[DzF]-N2X->[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. 099145164 16 201139371

BONA

(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 the method comprising 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 Into 099145164 17 201139371, a condensation reaction is carried out to form an "asymmetric coupler dimer". [CpC]-CONH-Ar-NH2+[CpD]-COX — [CpC]-CONH-Ar-NHCO-[CpD] [2] The coupling agent residue of the two, together with the diazo component E (formed after the reaction) Part of DzE) is coupled. [CpC]-CONH-Ar-NHCO-[CpD]+2[DzE]-N2X —[DzE]-N=N_[CpC]-CONH-Ar-NHCO-[CpD]-N=N-[DzE] An example of the reaction mechanism of the above general formula (III) is given. 099145164 18 201139371

(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 (1 v) 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]-N2X+[CpD]-COOH-[DzF]-N=N-[CpD]-COOH 099145164 19 201139371 [2] A coupling agent (Q (the residue is [CpC])" coupling amine substrate Condensation reaction with a sulfhydryl-based derivative of "monoazo dye-acid retardation" to form a "pigment coupling agent". [DzF]-N=N-[CpD]-COX+[CpC]-CONH-Ar- NH2 [DzF]-N = N-[CpD]-CONH-Ar-NHCO-[CpC] [3] The "pigment coupling agent" is coupled with the diazo component E (the portion where DzE is formed after the reaction).

[DzF]-N=N-[CpD]-CONH-Ar-NHCO-[CpC]+[DzE]-N2X -^[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. 099145164 20 201139371

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-deuterated aniline, 2-mercapto-4-nitroaniline, 2-decyloxy-4-nitroaniline, 2,5-dimethoxy-4-nitrated aniline, 2,5-diethoxy-4-nitrated aniline, 2,6-dimethoxy-4-pyramine, 2-cyano-4- 099145164 21 201139371 Determining stupid amine, 6-chloro-2- Cyano group _4. Determining stupid amine, 4-amino-Hi-cyano-nitrobenzene, 2. Deconstructing small naphthylamine, 4-confirmation-1-cylinamine, 2-amino-5-deconified diphenyl ketone, 4-amino-4'-nitrated-diphenyl sulfide, 2-amino--5-nitrated pyridine, and the like. The nitro group of the above coupling agent carbonyl (nitro)allyl decylamine is reduced to form a "coupling agent (amino) propyl propylamine", followed by further reaction to form an asymmetric spirulina pigment. The diaryl diamine residue of the di-carbon dye of the polyazo dye is corresponding to the above nitroallylamines, for example: oblique phenylenediamine, 2-gas-1,4-phenylenediamine , 2,5·dichloro], 4_deshenamine, methyl-1'4-phenylenediamine, 2'5-dimethyl-phenylenediamine 2-methoxy , 4_ phenylenediamine, 2,5-dimethoxyl 1,4-diphenylamine, 2,5-diethoxy 1,4- 4 1,4-diamine, 2 _-1,4· Diamine, 2-gas-5-methyl-1,4-phenylenediamine, 2,6-digas·M•Standing diamine, 2_Alityl_M•phenylenediamine, 6-chloro _2_ atmosphere M_ stupid diamine, 5 · desert _ 3-cyano-1,4-phenylenediamine, 1,4-diaminocaxene, 1,2-diaminonaphthalene, 2, 5-aminodiyl-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 heavy gas component F (the portion where the [D z F ] is formed after the reaction) are based on the conventionally known diazo component, and the molecular skeleton system can be used. For example, it has 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 the scale may also be The substituents exemplified. For example, the nonionic substituent is, for example, a condensed (carbon number: 1 to (9) group, anoxane (carbon 099145164 22 201139371 number: 1 to 10) group, a trifluoromethyl group, a halogen group, a nitro group; an alkyl sulfonium group; Alkylsulfonyl, alkylsulfonium diamine, phenylsulfonyldiamine, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoamido, aniline carbonyl, etc.; The substituents are, for example, a carboxyl group, a sulfonic acid group, a sulfate group, a phosphate group, etc.; and the cationic substituents are, for example, an amine group, an alkylimino group, a hydroxyalkylimine group, a monoalkylamine. a bis(hydroxyalkyl)amine group, a quaternary ammonium halide group, etc. The use of an allylamine or a heterocyclic amine which selectively introduces one or two or more identical or different substituents is also asymmetric as described above. The method for synthesizing the polyazo dye is the same as the case where the same one is used and the case where it is used differently. The hydrophobic diazo component having no ionic group is a conventionally known diazo forming tool such as the present amine. , methylamine (ο-, πι- or p_), 2,4-dinonanilide, 3,4-dimethylaniline, 2-methoxy-5-mercaptoamine (para cresidine) , methoxyaniline (ο-, m- or p-), aminophenol (〇-, m- or P-), nitroaniline (〇-, m- or p-), chlorinated aniline (〇) -, m- or p-), 2,5-dichloromoutamine, 3,4-dichloroaniline, 3,5-dianiline, 2,4,5-triseoaniline, 2-chloro-4- Nitroaniline, 5-chloro-2-nitrated aniline, 2,6-di-gas-4-nitrated aniline, o-fluoroaniline, 2,4-difluoroaniline, m-trifluoromethylaniline, 2-gas-5-three Fluoromethylaniline, 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-methoxy Stupid and thiazole, 1-aminoindole, 2-aminoindole, o-(phenylsulfonyl)aniline, 2-ethylsulfonyl-5-trifluoromethylaniline, 4-benzylsulfonate Keto-o-oxybenzene

S 099145164 23 201139371 Amine, o-methoxy phenothiamine 4-sulfonyldiethyl decylamine, o-methoxyaniline _ 4-sulfoethyl, 6-benzoguanamine _4_dimethylaniline, 4, 4-Dichloro-2-aminodiphenyl ether, 4-benzoguanamine-2,5-di-f-anilide, 9-aminoacridine, 6-aminocarbazole, and the like. In the present invention, an asymmetric polyazo pigment which is a coupling of only the hydrophobic diazo component having no ionic group is referred to as "asymmetric polyazo pigment". Further, examples of the diazo component having an ionic group include o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 2-airaniline-3-sulfonic acid, and 4-chloro. Aniline-2-sulfonic acid, 4-chloroaniline-3-sulfonic acid, 2,5-dianiline _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-anisidine-2-sulfonic acid, 2-gas-p-toluidine-3-sulfonic acid , 2-chloro-p-toluidine-5-sulfonic acid, 4-a-m-decylaniline-2-sulfonic acid, 3-amino-6-chlorotoluene-4-sulfonic acid, 3-amino-6-gas 4--4-phenylbenzoic acid, 1-amino-8-naphthalenesulfonic acid, 2-amino-1-naphthoic acid, 4-amino-i-naphthalenesulfonic acid, 5-amino-1-naphthalenesulfonate Acid, 6-amino-1_naphthalenesulfonic acid, 5-amino-3-naphthalenesulfonic acid, 4-amino-5-hydroxy-2,7-naphthalene diacid, 1-amino-2-hydroxyl 4-naphthalenesulfonic acid, 6-amino-4-hydroxy-2··naphthalenesulfonic acid, 7-aminohydroxy-2·naphthalenesulfonic acid, amino-2-indolesulfonic acid, 1-amino- 5-蒽 绩 acid, 1-amino-8- sulfonic acid, amino carbazole acid, 9-amino benzoic acid, o-amine benzoic acid, p-aminobenzoic acid, and the like. Further, in the case of using an ionic group-containing diazo component, the ionic group of the asymmetric polyazo dye obtained may be a salt form β such as 099145164 201139371. The field ion is a sulfonic acid group. In the case of the alkali which is a counter ion, for example, an alkali metal hydroxide such as chlordane or potassium; a hydroxide of a cerium metal such as calcium, aluminum, zinc, magnesium, nickel or iron; ammonia; Or c) a base (CVC2.) amine, an alkanol (Cl~C10) amine, and an alkyl (Ci~C2〇) ammonium chloride. In the present invention, these asymmetric polyazo dyes having an ionic group are referred to as "ionic pigment derivatives". The asymmetric polyazo pigments described above can be used in the same manner as conventionally known pigments, such as dyeing, printing, painting, printing, pen writing, drawing, resin coloring, and ink jetting. Printing, electronic photo printing, electrostatic printing, or color filter pixel forming methods, and the like. These coloring agents can be used in various known applications, and can be used as known dyes, printing agents, paints, printing inks, stationery, enamelware, resin colorants, inkjet printing inks, and electrophotographic printing. A developer, an electrostatic discharge developer, or a color filter pixel forming ink. Further, the ionic pigment derivative using the above-described diazonium component having an ionic group is not limited to the above-described color materials of the respective processes, and can be used as follows. For example, t-crystals are crystallized or difficult to process, or in materials such as paints, printing inks, coffee or UV-curable inks, photoresists for color-passing films, or thermosetting acrylic inks. In the case of using an organic solvent dispersion coloring agent or a pigment used in the coloring solution (IV), it may be added as a material for the purpose of suppressing crystal transfer, suppressing crystal growth, improving dispersibility, and improving heat recovery. When the pigmented ionic pigment derivative is pigmented (pigmentation treatment) at 099145164 25 201139371, it is added to the pigment crude material (crude pigment) or the coarse particle pigment, and is also in the liquid pigment dispersion type color. By using an additional pigment and using an ionic pigment derivative, it is also possible to improve the dispersing performance and improve the stability of storage. This kind of growth as a pigment crystal prevents the age from dispersing mosquitoes. In contrast, the ionic pigment street bio-agriculture does not bathe in the presence of a medium... The W-processed biological material has a total of about 1 or less. The average number is 〇5~〇! 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 money-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 colored hair of the present invention preferably contains the above-mentioned asymmetric polyazo dye of the present invention. Depending on the application, it is preferable to contain an asymmetric polyazo pigment, and if necessary, further contain a known pigment, and the diluent medium is used, for example, organic solvent, mixed with water and water/hydrophilic organic solvent. The human solvent 糸 constitutes an obstructive medium; a polymerizable oligomer, a condensed liquid medium composed of a polymerizable monomer; an oligo, an oligomer, a fat medium composed of a synthetic resin, and/or a coating material Containing: a group consisting of: a thermally heteropolymer, a polymer, a counter-touch, a poly-monomer, and a cross-linking agent: one or more (four) materials are selected as needed. Body squeegee powder, low molecular dispersant, hardening trending coloring agent. Hardening catalyst, polyfiber, etc., modulating 099145164 26 201139371 Furthermore, preparing a coloring agent a temple containing the above asymmetric polyazo pigment is prepared in advance to highly disperse the high concentration of the desired pigment in the dispersion medium. Concentration pigments and kings can be used to make the production of colorants easier. The liquid 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" (master P〇wder) according to the form. (The following is a case where these are collectively referred to as "base color"). Preferably, the primary colors are in the asymmetric polyazo dye, and if necessary, the necessary pigments are further added, and it is preferred to use a suitable liquid medium, a polymerizable liquid medium, a resin medium in which a coloring agent is blended, It is preferable to further use a polymerization system dispersant or a low molecular dispersant as a dispersing aid as needed. 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 the 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 with a conventionally known additive such as a dispersion aid, a smoothing agent, an adhesion agent or the like as needed. As a resin binder for a coating film forming material (referred to as "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 the baking type resin adhesive agent is, for example, a resin binder used for image recording materials such as printing dyes, paints or printing inks, stationery, ink jet printing, electrophotographic printing, and electrostatic printing. On the other hand, the photosensitive resin binder is a photosensitive resin binder used in various coating materials such as ultraviolet curable or electron beam 099145164 27 ^ 201139371, (iv), printing ink, inkjet ink, and the like. * The meaning of the warm-drying type or the paint-type resin binder is, for example, a vinyl resin such as a synthetic rubber resin, a propylene resin, a stupid vinyl (co) polymer, or a polyethylene butyl resin; A resin, an amine resin, a polyglycol resin, a polyamine phthalic acid resin, a acrylic acid urethane carboxylic acid resin, a soluble polyamine resin, a soluble (tetra) imine resin, and a soluble resin Polyamidoximine resin, soluble polyester quinone resin, alkyd resin, amino alkyd resin, epoxy resin, gasified rubber resin, Shishi resin, with fat, cellulose acetate a resin, a nitrocellulose resin, a hydroxyethyl cellulose, a water-soluble salt of a styrene-maleate copolymer, a water-soluble salt of a (mercapto) acrylate-based (co)polymer, and a water-soluble salt The amino acid-based alkyd resin, the water-soluble amino polyester resin, and the water-soluble polyamine resin may be used singly 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 system, an isolactic acid vinegar or an epoxy 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, sensitization 099145164 28 201139371 Polyurethane resin, photosensitive polyimide resin, etc.; and unsaturated polyester resin, polyester acrylate resin, poly epoxy acrylate resin, polyuric acid A binder such as an ester acrylate 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 as a coloring agent for forming a color filter pixel in a forming method thereof, and is used on a color filter substrate by a known method such as a photoresist method, a printing method, and a transfer. Forming a pixel by a method such as a paste method. For the color light-receiving sheet for a liquid crystal display or the image for an advertisement display, etc., the color-receiving object of the composition is such as a broken substrate or a plastic plate substrate. The asymmetric polyazo dye of the present invention can also be used as a plastic circuit for coloring plastics, such as thermoplastic plastics and thermosetting plastics which are well known in the art. Thermoplastic plastic (4) can be exemplified by: poly-section - meridian; polystyrene 'a' stupid = vinyl chloride, methyl propylene riding resin, polycarbonate, polyamide, polythermoplastic polyester, cellulose It is a plastic, a phenyl ether resin, a fluororesin (4), and the like. Further, the thermosetting property is, for example, an oxygen resin such as unsaturated poly 099145164, a pin fat, a polyamine ψW fat, or a melamine resin (10)W. In the coloring agent for plastics, as described above, a non-p-type polyazo dye or a pigment used in combination is used in advance, and a high-concentration household is dispersed in advance to form a (four) dispersion medium towel to form a high-concentration brittle dispersion = 29 201139371 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. In addition, the "parts" and "%" in the text are based on the quality standard without special statement. [Synthesis Example 1: Synthesis of coupling agent amine matrix] 〇) "Combination of nitro group" according to the common law' In 188 parts (1.0 moles) of 3-hydroxy-2-naphthoic acid (hereinafter abbreviated as γβονα), 138.1 parts (1.0 mol) of 4-nitroaniline was suspended in toluene, and phosphorus dichloride was dropped and carried out. 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, and the mixture was dissolved and dissolved by sodium hydroxide, and after filtration, the solution was added to acetic acid 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 a "coupling agent nitro group _ 丨. Similarly, the carboxylic acid (hereinafter referred to as "coupling_acid") of the coupling agent in the i-th column of Table i, Condensation with the _yl-ylamine in the second column, and the "coupler nitro group" described in the third column is obtained. 099145164 30 201139371 Table 1: Coupler; 6 Synthesis, mass, (mole) Number) ----- Product name, yield, yield nitroallylamine ------ "Coupling agent nitro" Material name (mole) Product name share (%) - Chlorine - 4- Confirmation of stupid amine 172.6 (1.0) Coupler 颂 base-2 311.8 (91%) • - gas 4-nitrated aniline ------ 207.0 _ (10) Coupler substrate - 3 339.4 (90%) Methyl-4-nitrated aniline 152.2 (1〇) coupling agent nitro group _4 296.5 (92%) "coupling carboxylic acid" material name

BONA BONA (b) Synthesis of "Coupling Amine Matrix" In 4,000 ml of methanol, 308.2 parts (1.0 mol) of "coupling agent nitro 1" obtained in the above (a) was charged, and sodium hydroxide was added. After the dissolution, concentrated hydrochloric acid was dropped to precipitate the precipitate to be fine. According to the usual method of iron powder reduction, 344 parts of reduced iron was added, concentrated hydrochloric acid was added dropwise, and the mixture was refluxed for reduction for 1 hour. Cool to room temperature and add more concentrated hydrochloric acid, _ % minutes. The resultant was filtered, and washed with methanol to obtain a methanol paste of an amine base hydrochloride. Then, 'filling the container with methanol 8, passing through the mixture... while mixing, adding the sodium hydroxide according to the above-mentioned age, adding sodium hydroxide, and then adding concentrated hydrochloric acid to dissolve the acid. ,filter. The paste of the above amine matrix hydrochloride was dispersed in the liquid of the container to neutralize _PH9.〇~9.5 ’ to obtain 256 parts of the aryl group. In the yield, the coupling agent with the amine group is called "the coupling agent amine group is described as "the same, and the nitroplast J of the 099145164 201139371 mixture obtained in Table 2 above is obtained. The "coupling amine substrate" described in the second position is obtained. Table 2: Synthetic filling material name, mass, (mole number) of the "coupler amine matrix" Product name, yield, yield r coupling agent nitro group. J "Reagent amine substrate" obtained by reduction —----- Parts of the product name (%) Coupler nitrobenzene_2 342.7 (1.0) Coupler amine matrix-2 284.6 (91%) Coupler nitro-3 - 377.1 (1,0 ) coupling agent amine matrix-3 312.4 (90%) coupling agent nitro group _4 322.3 (1.0) coupling agent amine matrix-4 268.9 (92%) [synthesis example 2: synthesis of "pigment carboxylic acid"] (a) 2 The diazotization of 5-dichloroaniline is carried out according to a conventional method, and 260 m of water and 32.41 parts of 2,5-dianiline (0.20 mol) are added together in a diazotization reaction apparatus, and 74 7 parts of concentrated hydrochloric acid is used. Acidic suspension. 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" Water (2, 〇〇〇ml) was added to the coupling reaction apparatus according to the usual method, and BONA (37.62 parts, 〇.2 〇mol) was added. After cooling to 53⁄4 or less, the diazo liquid of 2,5-dichloromoutamine obtained in the above (a) was slowly injected, and the pH was adjusted to 7. 〇 to 7.5 with a 1% 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 an azo dye of carboxylic acid 68.6 099145164 32 201139371 parts. The yield was 95%. Hereinafter, several hydrazine dyes (4**((2,5-diphenylphenyl)-azo)-3-hydroxy-2-naphthoic acid) are referred to as "coloring acid-1". Similarly, the "coupling agent tickling" 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. Table 3: Name, quality, (mole number) of the synthetic filler material of "pigmentary tannic acid" Product name, yield, yield "Coupling agent carboxylic acid J Diazo component "Pigment carboxylic acid" Material name (mole) Material name (mole) Product name share (%) BONA 37.62 (〇-2) 2-chloro-5-trifluoromethylaniline 39.11 (0.2) Pigment acid-2 74.2 (94%) HBCA 55.46 (0.2) Anthraquinone 27.62 (0.2) Pigment acid-3 76.8 (90%) Further, the above "HBCA" means 2-p-benzo[a]-flavored porphyrin acid. [Synthesis Example 3: Synthesis of "Pigment Coupling Agent"] In the same manner as in Synthesis Example 1 (a), 2,000 ml of vaporized benzene was charged into a reaction apparatus, and then charged in Synthesis Example 2 (b). 72.23 parts (0.20 moles) of the pigment acid-1" and 55.65 parts (0.20 moles) of the "coupler amine matrix-1" obtained in the synthesis example 1 (b), and phosphorus trichloride was added dropwise. Then, the temperature was raised to ll 〇 ° 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 decyl alcohol. Next, the obtained reaction product was added to 4,000 ml of decyl alcohol, and sodium hydroxide was further added thereto to dissolve, and the insoluble portion was filtered. Then, acid was added to precipitate, and the mixture was filtered, washed with decyl alcohol and water, and dried to obtain 94 parts of an azo dye-bonded coupling agent. Yield system

S 099145164 33 201139371 76%. Hereinafter, the obtained azo dye-bonding coupling agent is referred to as "the same as the dye-like agent", and the "coupling_matrix" described in the "color (4) column described in the fourth block of Table 4 is condensed to obtain "1". "Pigment coupling agent" in the second. Table 4: Synthesis of "Pigment Coupling Agent" Filling material name, mass, (mole number) Pigment carboxylic acid "Coupling amine base" Material name (mole) Material name Pigment acid-2 78.94 (0.2)

Coupler Amine Matrix-] Pigment Acid-1 72.23 (0-2) Coupler Amine Matrix-2 55.65 _(〇ϋ ~62S4 (0.2) Pigment Acid-1 72.23 (0.2) Coupler Amine Matrix-3

Pigment acid-1 72.23 (02) coupling agent amine matrix-4

Pigment acid-2 78.94 (0.2) coupling agent amine matrix-4

Pigment Acid-3 85.28 (0.2) Coupler Amine Matrix-1 55.65 (0.2) "Pigment Coupler Product Name Pigment Coupler 2 Pigment Coupler_ Pigment Coupler_4 Pigment Coupler_5 Pigment Coupler_6 Pigment Coupling agent - Yield (Synthesis Example 4: Synthesis of "Asymmetric Coupler Dimer"] In the same manner as in Synthesis Example 3, in the reaction apparatus, 2,000 ml of gasification was filled in, and then 2-base was charged. -11H-benzo[a]〇^_ ^ ! 55.46 parts (0.2 mol) of the acid (HBCA), and 55.65 parts of the "human agent amine matrix-1" obtained according to the synthesis example 1 (b) (0.20 mo Ear), drop phosphorus trichloride and heat to 110. (:, stirring for 8 hours, and carrying out a condensation reaction. Cooling to normal temperature 'filtered' and then washing with gasified benzene and methanol. Further dissolved in alkali methanol 98, 24 (75%) 101.0 ill%) 103.5 Ζ5 %) 96.6 (2^%) 99.0 CM%) 103.025%) 099145164 34 201139371 The acid was precipitated by adding acid, washed with decyl alcohol 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-air aniline 12.76 parts (0.10 mole) of 2-chloroaniline in a diazotization reactor according to the usual procedure The diazotization reaction. It was confirmed that the diazotization reaction was completed, and the excess sodium nitrite was decomposed by the amine acid, and filtered to obtain a diazo liquid of 2-aniline. (b) Synthesis of "Asymmetric Polyazo Pigment" In a coupling reaction apparatus, nitrobenzene 1,4 〇〇 ml, and 62.14 parts of "Pigment Coupler-1" obtained in Synthesis Example 2 were loaded. .1〇莫耳), cooling to 5〇c or less, and slowly adding a diazo liquid of 2-chloroaniline obtained in the above (a) to carry out 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 different diazo components. The yield was 95% and the hue was red. Hereinafter, the obtained double nitrogen pigment is referred to as "asymmetric polyazo pigment-1 J 〇", and the "pigment coupling agent" described in the first column of Table 5 and the diazo component described in the second column are described. The diazotization was carried out and the coupling reaction was carried out to obtain the "#symmetric polyazo pigment" described in the third column. 099145164 35 201139371 Table 5: Synthetic filling material name, mass it, (mole number) of the "asymmetric polyazo pigment" Product name, yield, yield "Pigment coupling agent" Diazo component "Asymmetric polyazo Pigment J ______ Material name (mole) Material name - (mole) —---- Product name share (%) Color tone coupler-2 65.50 (0.1) 2-air aniline 12.76 (0.1) Asymmetry Polyazo pigment-2 V /u/__ 74.6 (94%) --- Red pigment coupler-3 65.59 (0.1) 2-aniline aniline 12.76~ (0.1) ------- Asymmetric polyazo Pigment-3 /u/ 73.9 (93%) Red fid 12.76—(01) —-- —— Pigment coupling agent -4 .ui (0.1) 2-Az-aniline asymmetric polyazo pigment-4 79.6 (96%) Red Pigment Coupler-5 63.54 (0.1) 2-Veaniline 12.76 (0.1) ------ Asymmetric Polyazo Pigment-5 73.5 (95%) Red Pigment Coupler-6 66.70 (0.1) 2-Gas Aniline 12.76 (0.1) Asymmetric polyazo pigment-6 75.9 (94%) Red pigment coupler-7 68.67 (0.1) 2-aniline aniline 12.76 (0.1) Asymmetric polyazo pigment-7 75.9 (92%) black Asymmetric coupler dimer-1 53.76 (0.1) 2-Veaniline 25.52 (0-2) Asymmetric polyazo pigment-8 75.8 (93%) Black [Synthesis Example 6: Synthesis of "asymmetric dye derivative") (a) Amine sulfonic acid Diazotization The diazotization of p-aminobenzenesulfonic acid 17.32 parts (0.10 mol) was carried out in a diazotization reaction apparatus 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 p-aminobenzenesulfonic acid. (b) Synthesis of "Asymmetric Pigment Derivative" According to the usual method, 4,600 m of sterol and 66.7 parts (0.10 mol) of "Pigment Coupler-6" are charged in the coupling reaction apparatus, and cooled to 5~l 〇 ° C, slowly add the diazo solution of the aminobenzene sulfonic acid obtained according to the above (a), and carry out a coupling reaction. Indeed 099145164 36 201139371 The completion of the reaction is completed, and the acidity is formed by dilute hydrochloric acid. After washing, drying and drying, a total of 81·9 parts of the asymmetric double nitrogen pigment derivative having a rhein group on the unilateral dye residue are obtained. The yield was 96% and the color tone was motley. Hereinafter, the asymmetric double nitrogen dye derivative having a single-sided acid group is referred to as "pigment derivative-1". Similarly, the "pigment coupling agent" described in the 1st and 3rd columns of Table 6 was coupled with the diazo component described in the second column to obtain the "symmetric dye derivative" recorded in the third column. "." Table 6: Synthesis of "Asymmetric Pigment Derivatives" Filling Material Name, Mass, (Mole Number) Diazo Composition

Pigment Coupler-1 = ^; 07·1) 2 Asymmetric Pigment Derivative-2 The following is a chemical name of the following example. ^

Product name, yield, yield, asymmetric pigment derivative, product name

37 S 1 Asymmetric polyazo pigment-1 >, Ν (1,4 phenyl)-4-((2-indolyl)azo)_3_ carbyl_2_Craft carbonamine)- 4'·((2,5-dichlorophenyl)azo)·3,_transyl 2,_cai (tetra)amine) 2 asymmetric polyazo pigments 2 Ν,Ν (1,4 extension base )-4-((2_乳笨基)Azo)]·Transyl 2•Cetamine W5-Tris(4-)ylphenyl)Azo)_Base 2,Naphthalene Carbonate 3 Asymmetric Polyazo Pigment- 3 099145164 201139371 N,N'-(2-Chloro-1,4-phenylene)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4' -((2,5-dichlorophenyl)azohydroxy-2·-naphthalenecarbiniumamine) (4) Asymmetric polyazo pigment-4 N,N'-(2,5-dichloro-1, 4-phenyl)-4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-((2,5-dichlorophenyl)azo) -3'-hydroxy-2'-naphthalenecarbiniumamine) (5) Asymmetric polyazo pigment-5 N,N'-(2-methyl-1,4-extended base)-4-((2 -chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbinium)-4'-((2,5-dichlorophenyl)azo)-3'-hydroxy-2'-naphthalenecarbonium Amine) (6) Asymmetric polyazo pigment-6 N,N'-(2-methyl-1,4-extended base)_4-((2-chlorophenyl)azo)-3-hydroxy- 2-Qin carbonic amine)-4'-((2- Chloro-5-difluorodecylphenyl)azo)-3^lightyl-21-hhenylcarbendamine) (7) Asymmetric polyazo pigment-7 N,N'-(1,4-phenylene) 4-((2-chlorophenyl)azo)-3-hydroxy-2-naphthalenecarbiniumamine-indole-((4-nitrophenyl)azo)-2'-hydroxy-11Ή- Benzo[a]carbazole-3'-carbolamine (8) asymmetric polyazo pigment-8 N,N'-(1,4-phenylene)_4-((2-chlorophenyl) couple Nitro))-3-hydroxy-2-naphthalenecarbamine)-indole-((2-chlorophenyl)azo)-2'-hydroxy-11-benzo[a]carbazole-3'-carbonamide (9) Asymmetric pigment derivative-1 Ν,ϊ^-(2-mercapto-1,4-phenylene)-4-((4-sulfophenyl)azo)-3-hydroxy 099145164 38 201139371 -2-naphthylcarbamine)-4,-((2-chloro-5-trifluoromethylphenyl)azo)_3'-hydroxynaphthalenecarbiniumamine) (10) Asymmetric pigment derivative- 2 N,Nf-(l,4-Extended phenyl)-4-((4-sulfophenyl)azo)-3_hydroxy_2-naphthalenecarbocene)-4,-((2,5 -Dichlorophenyl)azo)-3,-hydroxy-2'-naphthalenecarbiniumamine [Example 1: Baking paint for metal products] "Asymmetric polyazo pigment-1" obtained in Synthesis Example 5 5 parts, and an alkyl methacrylate having a hydroxyl group and a carboxyl group - Ethylene-ethyl acetate solution copolymerization reaction Styrene acrylic resin 45 parts (solids content 50%) of the assembly constituted of glass beads is added according to an ordinary method using a paint shaker for eight scattered. Next, a methoxymethyl melamine cross-linking agent (solid content: 5 noisy parts, anti-separator 0·1 part, and 44.9 parts of xylene) was added, and acryl benzene for red metal products was further prepared. Ethylene coating. After that, the paint spray is applied to the metal product, and the paint is applied, and the red coating of the metal product is applied to the shell. In addition, the aluminum powder is used to form the acrylic paint for the metal product. A red paint which is excellent in weather resistance and excellent in weather resistance is obtained. [Example 2: Printing paste for woven fabric] The "asymmetric polyazo pigment, 2" 25 obtained in Synthesis Example 5, and a nonionic phthalocyanine dispersant are used. Defoamer 丨, and water "64f, part, water I. raw pigments. Then, in the reaction (four) frequency 7 basis 4%) 25 parts, defoamer G. 5 parts, dispersant 1 part, water by glue (solid dispersion emulsifier 3 parts, turpentine 38 parts, and water: drop type 099145164 ,, so that

39 S 201139371 A paste-like red paste in which an azo pigment was dispersed was obtained by using 20 parts of the aqueous pigment dispersion obtained above. 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 12 (rc for 15 minutes to obtain a red printed matter. [Example 3: Polyurethane coating agent] Carboxyl polyether polyol diphenylmethane diisocyanate polyurethane milk white ketone ethyl ketone dispersion (solid content: 3% by weight) 1 part by weight polyether polyol diphenyl decane diisocyanate polymerization 5 parts of a carbamate ethyl ketone solution (solid content: 50%), and a polycarbodiimide crosslinking agent (solid content: 20%) 2.5 parts are thoroughly mixed, and the compound 5 is added thereto. 0.5 parts of "asymmetric polyazo pigment-3" obtained, and an asymmetric polyazo pigment paste which is kneaded with 1 part of an adipate plasticizer, and thoroughly mixed to prepare a red polyamine a formate coating liquid, which is coated on the surface of the polyester woven fabric to be dried at about 200 g/m 2 ' to obtain a red fiber processed product. [Example 4: aqueous intaglio ink] will be obtained according to Synthesis Example 5. 15 parts of asymmetric poly-arsenic pigment _4", obtained from polycarbonate polyol and aliphatic isocyanate Retardant polyglycolic acid g water-based resin (solid content: 30%) 60 parts, water-dispersible butterfly (solid content: 30%) 5 parts, defoamer 1 part, polycarbodiimide cross-linking agent (solid content: 5〇0/.) 5 parts, and 14 parts of water were blended to prepare a red water-based gravure ink. Similarly, PB15: 3 (phthalocyanine blue pigment), ργ74 (monoazo yellow 099145164) was used. 40 201139371 Color pigments), and ΡΒΚ: 7 (carbon black pigment), prepared with blue, color, and ink water-based four-color inks, respectively. Using the four-color printing ink obtained, printing on polyethylene, poly_ A transparent, non-colored plastic film such as a polyester or a nylon is obtained. A beautiful printed thin mold is obtained. [Example 5: Resin molding] 5 parts of asymmetric polyazo pigment, titanium oxide white pigment obtained in Synthesis Example 5 2G parts, and a poly 6-ene resin powder 75 used as a pigment dispersant, and a J-Korean blender (powder high-speed mixer) is used to obtain a powder coloring agent (dry color material). 1 part of the obtained powder coloring agent is blended and used in (10) parts of polybutylene terephthalate (PBT) resin particles. The blender was mixed and the red resin pellets were formed by the extruder, and the obtained red pellets were taken out to obtain a red PBT resin formed panel excellent in pigment dispersibility. [Example 6: Transparent Resin-formed sheet] 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 The mixture was mixed with a Han Su blender, and red resin particles were formed by an extruder. The obtained red particles were molded by an inline screw type injection molding machine to obtain a red transparent acrylic resin excellent in pigment dispersibility. Forming plate. The same change was made to an acrylic resin, and the polycarbonate resin particles were colored by using a polycarbonate masterbatch red masterbatch pellet, and shaped to obtain a red transparent polycarbonate formed panel excellent in pigments and scented 099145164 41 201139371. [Example 7: Sperm-spun yarn of the stock solution] The "Asymmetric Multi-Bad Pigment _7" % obtained in Synthesis Example 5, and the ethyl bis-hard-cranked amine powder as a pigment dispersant, The mixture was mixed using a Han Su blender to obtain a dry color material (color) of 5 % by weight of the pigment. (4) Mixing the obtained dry color material [o rubbing in 99.0 parts of Juaiguishuyue ^ granules] using a Han Su blender, and then mixing it with a heart-type 40 m/m extruder to form 〇.5 % red resin pellets. The obtained red resin pellets were spun by a melt spinning machine to obtain a bright red polyene liquid stock dyed yarn excellent in pigment dispersibility of the fiber Danny [Example 8: digital electronic printing] (1) ( Preparation of a resin composition containing a pigment) 30 parts of "asymmetric polyazo/material-4" obtained in Synthesis Example 5 as a red pigment, and bisphenol octa-bis (propylene glycol ether) With 70 parts of the phenanthrene resin (average molecular weight: about 15,000), the polyester masterbatch for preparing the red pigment was completed by using a twin roll machine. In addition, except for the "asymmetric polyazo pigment field" obtained by the use of 2 恳 black pigment in the synthesis example 5, the polyester masterbatch of the black pigment was prepared in the same manner as described above. PB15 of the blue pigment: 3, and the use of the yellow pigment, except for the above, respectively, the blue and yellow polyanthracene are obtained ~ (2) Scenery> The modulation of the coloring composition for recording, and the full color TV ;5 ^ ·,, 'Print of the film

Then, according to the formula (parts) in Table 7 below, each color obtained according to the above, X 099145164 42 201139371 = material two-blown exposure, and the fault-type salt-based negative charge control agent, Broken, then, she smashed slightly, and used the technique of coloring composition for the image recording of the micro-powder Dongqing of the granules. Adding a fluidized agent of colloidal magnetic iron powder to form a domain color, magenta, ^ carrier

Electronic photo dry developer. Using the electronic photo-type full-color thunder: printing of the printing plate 2, obtaining the (four) full material (four) printed matter. Table 4 (4) Table 7: Composition of Developer----1 [Example 9: Color Du (I) (Color Modulation, Preparation of Pigment Dispersion for Light Film) (Modulation of Red Pigment Dispersion) Symmetrical poly-gas pigment. 2" 20 parts, "Asymmetric pigment derivative 2 parts, (4) methyl group acid S (1) group called acid group) thiophene ketone vinegar copolymer (Mo Erbi: 6 〇: 2 〇 · 击曰ϋ·20, weight average molecular weight 30000) 099145164 43 201139371 hereinafter referred to as "bzMa_MAc_hema copolymer") 15 parts, 4 parts of cationic system dispersant, and PGMA (59 parts), dispersed by a continuous-disperser to obtain red (four) Sub-ship (hereinafter referred to as ";|Dispersion-1"). , 'I 邑 pigment is the same as (1) above, but replaces asymmetric polyazo pigment _2, changes PR254 (dioxane and ^ slightly red pigment), and replaces "non-nickname color: derivative-1" Instead, use "Asymmetric Pigment Derivatives _2" and disperse to obtain red (iv) dispersion (hereinafter referred to as "red (four) dispersion _2" (, 彔 color, color, purple pigment dispersion) ) Same as (1) above, but instead of asymmetric polyazo pigment_2, used instead of p(10)(10) copper bronze green pigment), PB15:6 (ε(tetra)cyanine blue pigment), state 5〇 (gold complex yellow pigment) In the fine (iv) cultivating purple pigment), a pigment composition of a pigment derivative having a known base is added, and a pigment dispersion liquid having a pigment content of 2 G% is obtained in the same manner as in the above (1). Hereinafter, the knife is called, the green pigment dispersion "", the "blue pigment dispersion", the "yellow pigment dispersion VII, and the "purple pigment dispersion-1". (2) (modulation of photosensitive photoresist ink of each pigment) To form red (11), green, and blue (B) pixels on the glass substrate of the color filter, the red color is prepared according to the above (1) Pigment dispersion 2 color, and, color, blue, color, purple pigment dispersion, according to the formulation (parts) of the following Table 8 to obtain photosensitive red edge ink, photosensitive (four) color photoresist ink, photosensitive blue Color photoresist ink 099145164 201139371 Table 8: Composition of photosensitive photoresist ink Sensitive red photoresist ink Sensitive green photoresist ink Sensitive blue photoresist ink Red pigment dispersion-1 40 — — Red pigment dispersion-2 60 — — Green Pigment Dispersion-1 — 60 — Yellow Pigment Dispersion-1 — 40 — Blue Pigment Dispersion-1 — — 80 Purple Pigment Dispersion-1 — — 20 Photosensitive Acrylic Resin Varnish 50 50 50 TMPTA 10 10 10 HEMPA 2 2 2 DEAP 1 1 1 PGMA 37 37 37 Total 200 200 200 In the above, TMPTA means trishydroxypropyl propane triacrylate; HEMPA means 2-hydroxyethyl-2-methylpropane - 1-ketone; DEAP means 2,2-diethoxybenzene Ketone. (3) (Formation of RGB pixels 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 applied at 1,200 rpm. 5 seconds of spin coating. Then, pre-bake for 10 minutes at 80 ° C, will have

S 099145164 45 201139371 A mosaic-like mask is placed on the coated surface of a glass substrate, and exposure is performed by an ultra-high pressure mercury lamp at a light amount of 100 mJ/cm 2 using a proximity exposure machine. Then, development and cleaning were carried out by using a dedicated developer and a dedicated cleaning to form a red mosaic pattern on the glass substrate. Then, 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, and is excellent in light fastness and heat resistance, and has excellent light penetration properties. It is excellent as a color filter for liquid crystal color display. nature. (Industrial Applicability) According to the present invention described above, 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 by the coloring, co-precipitation, or mixed crystal form of different plural pigments can be achieved, and the physical properties of the pigments such as crystallinity and microparticle stability can be improved by using the same intramolecular Novel pigment systems having different chromonic molecular structures can be expected to have novel pigment systems that achieve pigment properties such as new hue, new crystallinity, and particle properties. Furthermore, by performing a pigment treatment on an asymmetric 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 the organic solvent-based pigment-dispersed color pigment dispersion, the dispersion of the viscosity of the dispersion is 099145164 46 201139371 low, and the dispersion stability, long-term preservation stability and other performance enhancers, so it is better

S 099145164 47

Claims (1)

201139371 VII. Scope of application for patents · 1. Non-p-type (four) polyazo pigments, mutually different monoazo pigment residues (4) and monoazo pigment residues (8) using extended aryl poly(carbon amide (tetra) amide )) based on the lamp, the 'in which each single azo dye residue system, the coupler residue and the diazo splicer are coupled together to have a group selected from the group consisting of (1) to (3) below Molecular structure of asymmetric polyazo dye: (1) The residue of the coupling agent (c) of the monoazo dye residue (4) and the monoazo pigment residue (B) is the same as the residue of the coupling agent (c), and the diazo component is a molecular structure of a plurality of azo dyes coupled by different diazo components (E) and a diazo component (F); (2) respective monoazo pigment residues (A) and monoazo pigment residues (b) The coupler residue is a residue of the coupling agent (c) and the coupling_), and the diazo component is a polyazo dye molecular structure coupled by the same diazo component (E); (3) a monochromatic pigment residue (4) a residue of the coupling agent (C) and the coupling agent (D) different from the respective coupling agent residues in the monoazo pigment residue (B), and the diazo component is composed of different nitrogen components (E) Multi-nodal pigment molecular structure coupled with the diazo component (F). 2) The asymmetric polyazo dye according to the third aspect of the patent application, wherein the coupling agent used to form the residue of the coupling agent (C) or the coupling agent (D) has a coupling agent Selected from 纟3_ 基 么 蔡 carboxylic acid, praline-2-naphthoic acid, 2-yl -3- decanoic acid, 2- carbyl-3·di- benzopyrene, 2-hydroxycarbazole Carboxylic acid and 2-hydroxyl-11H_benzo[a].carbazole-3-carboxylic acid 099145164 48 201139371 The same or different coupling agents in the group formed. 3. If you apply for a patent scope! The asymmetric polyazo dye of the above-mentioned exoaryl poly(carboguanamine) group having no or having a substituent selected from the group consisting of a diphenylamine, a diaminonaphthalene, a diaminobiphenyl, and a double a group consisting of (amino)alkyl, anthracenyl bis(aminophenyl), bis(aminophenyl) sulfide, bis(aminophenyl)sulfonyl and diamine The residue of an aryldiamine in the middle. 4. The asymmetric polyazo dye according to item 3 of the patent application, wherein the above-mentioned extended aryl diamine has one to two or more substituents derived from an alkane (carbon number: 1 to 1) 〇), alkoxy (carbon number: 1 to 10), trifluoromethyl, halo; alkyloxycarbonyl, alkylsulfonyl, sulfonamide, alkyl sulfoamide Base, phenylsulfonyldiamine, alkylamine sulfonyl, aniline sulfonyl, amine carbonyl, benzoguanamine, alkylamine carbonyl, aniline carbonyl; carboxyl, sulfonate, sulfate, phosphoric acid Any one selected from the group consisting of an ester group; an amine group, an alkylimino group, a hydroxyalkylimino group, a dialkylamino group, a bis(hydroxyalkyl)amino group, and a quaternary alkanolammonium group, Or select the same or different two or more bases from the group. 5. The asymmetric polyazo dye according to claim 1, wherein the diazo component (E) or the diazo component (F) has no or a substituent and has an allylamine derived from The skeleton of the molecule, or the skeleton of the molecule derived from the heterocyclic amine. 6. The asymmetric polyazo dye according to claim 5, wherein the allylamine or heterocyclic amine has no or a substituent from the aniline, naphthalene 099145164 49 201139371 amine, amine ruthenium, Any one selected from the group consisting of aminoguanidine, aminodibenzofuran and aminocarbazole; and the substituent having the substituent described above is derived from an alkane (carbon number: 1 to 10) group, an alkoxy group (Carbon number: bis(9) group, trifluoromethyl group, halo group, nitro group; alkyloxycarbonyl group, alkyl sulfonyl group, amine sulfonyl group, alkyl sulfonyl diamine group, phenyl sulfonyl diamine group , alkylamine sulfonyl, sulfonamide, amine carbonyl, benzoguanamine 'alkylamine carbonyl, aniline carbonyl; carboxyl, sulfonate, sulfate, phosphate; amine, alkyl Any one selected from the group consisting of an imido group, a hydroxyalkyl imino group, a dialkylamino group, a bis(alkyl) group, and a quaternary alkyl group, or selected from the group Two or more bases which are the same or different. 7. - A method for producing an asymmetric polyazo dye" is an asymmetric polyazo color of the first application of the patent application scope Any one of the following (丨) to (3): (1) Π] reacting the buffer base of the coupling agent (C) with the terminal group dilute propylamine to form The coupling agent nitro group of the nitro coupling agent, [2] „ reduction of the nitro group to form a “coupling agent amine matrix”, [3] coupling the prepared coupling agent (C) to the nitrogen component (Ε) The "monoazo dye phthalic acid or acid halide derivative" is subjected to a condensation reaction with the "coupling amine substrate" obtained in the above [2] to form a coupling agent having a monoazo pigment. "Pigment coupling agent" [4] coupling the dye coupling agent to the diazo component (F) to obtain a residue having the same coupling agent (c) and a different diazo component (E) a method for asymmetrical polyazo pigment of a residue of a diazo component (F); (2) [1] a carboxyl group having a coupling agent (C) and a nitroallylamine are reversed 099145164 50 201139371 Forming a "coupling agent nitro group" belonging to a coupling agent having a nitro group, [2] reducing the Jing group to form a "coupling agent amine matrix", [3] making another standard The carboxyl group or the fluorenyl halide derivative of the prepared coupling agent (D) is subjected to a condensation reaction to form an "asymmetric coupling agent dimer", [4] to make the coupling agent residue and weight of the dimer The nitrogen component (E) is coupled to obtain an asymmetric polyazo pigment having a different coupling agent (c) and a coupling agent (D) residue and a residue of the same diazonium component (E). (3) [1] reacting a carboxyl group possessed by the coupling agent (C) with a nitroallylamine to form a "coupler nitro group" belonging to a coupling agent having a nitro group, [2] The nitro group is reduced to form a "coupling amine substrate", and [3] the separately prepared coupling agent (D) is coupled with a "monoazo dye carboxylic acid or a fluorenyl halogen" which emphasizes the nitrogen component (F), and the above [2] The obtained "coupling amine substrate" is subjected to a condensation reaction to form a "pigment coupling agent" which is a coupling agent having a monoazo pigment [4], and the dye coupling agent and the diazo component (E) are subjected to a condensation reaction. Coupling, thereby producing residues having different coupling agents (C) and coupling agents (D), and residues of different diazo components (E) and diazo components (F) Symmetric polyazo dye of the method. A coloring agent comprising the asymmetric polyazo dye of any one of claims 1 to 3 as a color material. 9. The coloring agent according to item 8 of the patent application, further comprising any of a liquid medium, a polymerizable liquid medium or a resin medium, and/or a thermoplastic polymer, a reactive polymer, Reactive oligomers, poly. | One or more selected from the group consisting of raw monomers and crosslinkers. 099145164 201139371 Film forming material. 10.1 A coloring agent containing a plurality of azo dyes as a color material, wherein the asymmetric second type of the illusion is == the sputum component (E) is composed of an anionic or a cation product =:= Asymmetric polyazo-derived asymmetric polyazo dyes derived from coupled ionic pigments. In addition, as a dispersing aid, it contains a ionic or chemical (I) with antiionic properties. The release medium contains an organic solvent. a bio-based compound as a dilute U. The coloring agent according to item 10 of the patent application, the agent is composed of an ionic pigment street organism, and the above dispersion-assisted symmetric polyazo pigment, the first of the divisions The diazo component of the non-form. 〇 "The use of ionic groups in the domain system. 12. The coloring agent dyeing agent, printing agent, coating" printing according to the first aspect of the patent application, the above coloring agent grease coloring agent, inkjet printing ink, electronic Zhaozhao =,, continuation tools, developer for tree printing, color filter, developer for film formation, and coloring method for electrostatic 13.--------------- Coloring agent, according to dyeing, printing, painting "printing δ or 10 resin coloring, inkjet printing, electronic photo printing, electrostatic printing, light film pixel formation method, choice, or shirt The method of coloring the article of claim 13 wherein the color filter pixel forming method is on a color filter substrate, using a photoresist method, Pixel formation by any of the methods of inkjet printing, printing, transfer, or pasting. 15. Coloring articles are colored according to the coloring method of claim 14. 099145164 53 2011393714. Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 099145164 2