TW201006833A - Trisazo compound, ink composition, recording method and coloring material - Google Patents

Abstract

Disclosed is a dye compound for black ink which has high solubility in media composed mainly of water and which is stable even when a high-concentration aqueous solution and ink are stored over a long term. The density of printed images is very high, and even if a high-concentration solution is used for printing, no bronzing occurs in the images, and black recorded images are provided with which all aspects of printed image durability, particularly light resistance and ozone gas resistance, are excellent. Also disclosed is an ink composition thereof. Trisazo compounds represented by general formula (1) or tautomers thereof or salts thereof are used as said dye compound for black ink. (In formula (1), group A represents a 2-naphthothiazolyl group, R1 represents a substitutable C1 to C4 alkyl group or the like, R2 represents a cyano group or the like, R3 and R4 independently represent a hydrogen atom, a sulfo group, or the like, R5 to R7 independently represent a hydrogen atom, a substitutable C1 to C4 alkyl group, or a substitutable C1 to C4 alkoxy group, or the like, and R8 to R10 independently represent a hydrogen atom, a substitutable C1 to C4 alkyl group, a substitutable C1 to C4 alkoxy group, a substitutable C1 to C4 alkylthio group, or the like.)

Description

201006833 VI. Description of the Invention: [Technical Field] The present invention relates to a novel trisazo compound or a salt thereof, an ink composition containing the same or a salt thereof, and a coloration produced by the compound or salt body. 1 [Prior Art] 之一 One of the representative methods in various color recording methods is to use the recording method of the inkjet printer to generate ink (4) to attach the recorded material (paper, film, Buwe, etc.). Come up and record. In this method, since the recording head does not directly contact the material to be recorded, the generated sound is small and quiet, and since it has the advantages of being easy to be miniaturized and high-speed, the method is rapidly popularized in recent years, and it is expected to have a large growth in the future. . In the inks used in the previous 'pens, felt pens, etc., and inks for inkjet printing, aqueous inks obtained by dissolving a water-soluble pigment in an aqueous medium are used. Further, in the aqueous inks, it is possible to prevent the ink from being clogged in the nib or the ink jet nozzle, and a water-soluble organic solvent is generally added. Further, for such inks, it is required in the industry to provide a recorded image having a sufficient concentration, which does not cause clogging of a pen tip or a nozzle, has good dryness on a material to be recorded, has less bleeding, and is excellent in storage stability. Further, in the water-soluble coloring matter to be used, it is particularly required in the industry to have high solubility in water and high solubility in a water-soluble organic solvent added to the ink. Further, the industry is required to have excellent fastness such as water resistance, light resistance, gas resistance 201006833, and moisture resistance. The term "gas resistance" refers to the resistance to the following phenomena: ozone gas or the like which is present in the air and has an oxidizing effect, which acts on the recording paper to cause discoloration or extreme color of the printed image. . In addition to the ozone gas, the oxidizing gas having such a function may be Ν〇χ, 〇, x, etc., but 疋, generally, in the oxidizing gas, the ozone gas system is further promoted; The main cause of discoloration or fading. Therefore, in the resistance to rolling, it is particularly preferable to pay the most attention to ozone gas resistance. In order to dry the ink and reduce the bleeding of the high enamel, the ink absorbing layer provided on the surface of the photographic inkjet paper is often made of a porous white inorganic material. Discoloration or fading caused by ozone gas is apparent on such recording paper. The discoloration or fading caused by the oxidizing gas is a characteristic of the ink jet image. Therefore, the improvement of the ozone gas resistance is one of the most important problems in the ink jet printing method. After 7th, in order to expand the use of printing methods using inks, the ink composition used in inkjet printing and the coloring matter of the I color body are strongly required to improve light resistance, _ ozone Gas, moisture and water resistance. The inks of various hues are prepared from various pigments, which are important inks for both monochrome images and full-color images. As such pigments for black inks, various proposals have been made by the manufacturer to date, but products which sufficiently satisfy the market requirements have not yet been provided. Most of the proposed pigments are azo pigments, and the biazo pigments such as cl Food Black 2 have poor color rendering, poor water resistance or moisture resistance, and insufficient light resistance or gas resistance. The extended azo dye usually has a problem of low water solubility and is liable to cause a br〇nzing phenomenon in which a portion of the recording material has a metal ruth, and has problems such as insufficient light resistance or gas resistance. In addition, in the case of gold-containing azo dyes which are also proposed by the industry, although there is also good light resistance, there are poor biosafety or environmental problems due to the presence of metal ions, and the ozone gas is rich. Very weak and other issues. As a black pigment for inkjet which is improved in ozone gas resistance which is the most important problem in recent years, for example, it is described in the patent document. However, the ozone gas resistance of these compounds did not sufficiently satisfy the market requirements and was insufficient in light resistance. Further, as one of the characteristics of the trisazo compound of the present invention, it is also cumbersome. The odor: compound of the ketamine skeleton is described in Patent Document 4 to 等. Patent Document 6 also discloses that there are no trisazo compounds, but these trisazo compounds are at the two ends of the linking group containing the azo structure, and the two benzopyrenes bite the net skeleton into the step-by-step bond. The symmetrical structure formed by the nitrogen structure is not disclosed as being similar to the asymmetric trisazo compound of the present invention. In addition, there is no use case as a black compound for ink for nozzle inks. As an example of the quaternary vaporized yttrium having an excellent ink repellency ink, a compound recorded in Patent Document 8 discloses that a black pigment for a nozzle ink which is water-soluble can be used. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-183545 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. 2 〇〇 〇ΐ ΐ ΐ [ 专利 专利 专利 专利 专利 专利 专利 专利 专利 517 517 517 517 517 517 517 517 〇 〇 〇 2004 2004 2004 2004 2004 2004 2004 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A trisazo compound or a salt thereof used as a dye in black ink, an ink composition containing the compound or a salt thereof as a pigment, and a color body produced by the compound or a salt thereof. [Technical means for solving the problem] The present inventors have intensively studied in order to solve the above problems, and as a result, * the specific trisazo compound can solve the above problems, thereby completing the present invention. - the invention relates to: a tris-azo compound or a tautomer thereof, or a salt thereof, which is represented by the following formula (丨), [Chemical Formula 1] ' 201006833 ( In the formula (1), R1 is a carboxyl group, an unsubstituted or carboxyl group-substituted C1 to C4 alkyl group, or an unsubstituted or sulfo group-substituted stupid group, and R2 is a cyano group, an amine formazan group, or a ring group. , R3 and R4 are each independently a hydrogen atom, a gas atom, an exact group, an unsubstituted C1~C4 alkyl group, or an unsubstituted C1~C4 alkoxy group; a ring substituted by r5 to r7' When the ring shown is not present, the benzene Φ ring 'is a naphthalene ring in the presence of a ring indicated by a broken line, and R5 to R each independently represent a hydrogen atom; a gas atom; a hydroxyl group; a sulfo group; a carboxyl group; an amine sulfonyl group; Sulfhydryl; unsubstituted C1~C4 alkyl; unsubstituted or substituted by hydroxy, unsubstituted C1~C4 alkoxy, hydroxy C1~C4 alkoxy, sulfo, or carboxy group~ By alkoxy; unsubstituted or substituted by hydroxy, sulfo, or carboxy, mono or di- to C4 alkylamino, unsubstituted, or a C4 alkylcarbonylamino group substituted with a hydroxy group or a carboxy group; an unsubstituted or N=_C1~C4 leucoyl group substituted with a hydroxy group, a sulfo group or a carboxy group; an unsubstituted or a benzene ring via a gas original* Unsubstituted C1~C4 alkyl, nitro, sulfo, or decyl substituted phenylamine; unsubstituted, or phenyl ring via a gas atom, unsubstituted C1 to C4 alkyl, nitro a sulfo- or carboxy-substituted benzhydrylamino group; or an unsubstituted, or a stupid ring, a gas atom, an unsubstituted phenyl group substituted with an alkyl group, a nitro group, a sulfo group, or a carboxyl group; a mercaptoamine group, a ring substituted by R to R, which is a naphthalene ring when the ring shown by the dotted line is not present, and a hydrogen atom in the presence of a ring represented by a broken line, and R8 to R1G independently represent a hydrogen atom; Hydroxy; sulfo, · 7 201006833 carboxy; sulfonyl; amine carbaryl; unsubstituted C1 to C4 alkyl; unsubstituted 'or hydroxy, unsubstituted C1 to C4 alkoxy, a ci~C4 alkoxy group substituted by a radical C1 to C4, an oxy group, a contiguous group, or a buffer group; unsubstituted, or via a hydroxy group, a sulfo group, or Substituted C1~C4 thiol group; unsubstituted or substituted by hydroxy, sulfo, or carboxy group; or di-C1~C4 alkylamino group; unsubstituted or substituted by hydroxy or carboxy group 1~C4 alkylcarbonylamino group; unsubstituted, or N'-C 1~C4 alkyl group substituted by hydroxy, contiguous, 0 or thiol; unsubstituted ' or benzene ring by gas atom, not Substituted C1-C4 alkyl, nitro, sulfo, or m-substituted phenylamine; unsubstituted 'or benzene ring via a gas atom, unsubstituted C1 to C4 alkyl 'nitro, sulfonate a benzyl hydrazino group substituted with a carboxy group or a carboxy group; or an unsubstituted or phenyl sulfonyl group substituted with a benzene ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group. An amine group, a group A unsubstituted or substituted thiazolyl group; a thiadiyl group; or a oxime group, wherein when the benzothiazolyl group has a substituent, it may have a gas selected from the group consisting of: Atom; sulfo; nitro; hydroxy; sulfonyl; unsubstituted C1 to C4 alkyl; unsubstituted, or via hydroxy, C1 to C4 alkoxy a sulfo group or a carboxy-substituted C1 to C4 alkoxy group; an unsubstituted or C1 to C4 alkylsulfonyl group substituted by a sulfo group, a sulfo group or a fluorenyl group; and an unsubstituted or benzene ring via a chlorine group a group substituent consisting of an atom, an unsubstituted C1 to C4 alkane, a nitro group, a sulfo group, or a fluorenyl substituted phenylsulfonyl group, when the thiadiazolyl or thiazolyl group has a substituent , may have 201006833 free choice: gas atom; sulfo-' / Schottky; hydroxyl; amine sulfonyl; base; and, unsubstituted, or via hydroxyl, C1 ~ C4 alkoxy, hydroxy Ci ~ C4 alkane a substituent in the group consisting of an oxy group, a sulfo group, or a carboxyl group substituted with a Cl~C4 alkylthio group). (2) The trisazo compound or the tautomer thereof, or the salt thereof, wherein the trisazo compound represented by the above formula (1) is represented by the following formula (2) ,

W _ [Chemical Formula 2]

(In the formula (2), the base A and the ring include the meanings indicated by broken lines).

And R1 to R1G, and a ring substituted by R8 to rig, both having the same formula as in formula (1), wherein the trisazo compound or the mutual variation thereof is represented by the above formula (1) )·The three mate

9 201006833 (in the formula (3), the meaning of the base A, R1 to γ) has the same as the formula (1) - as in the above 1) to 3) ^ Έ mn ^, ''丨 azo compound at the 丨An isomer, or a salt thereof, wherein the upper azo compound is represented by the following formula (4), and the coating [Chemical Formula 4]

(4) (In the formula (4), the groups A, R to r4, and R8 to R!0 have the same meanings as the formula (丨), and R and R each independently represent a hydrogen atom; unsubstituted.

The group, or 'unsubstituted, or substituted by a sulfo group or a hydroxyl group, C1 to C4 alkoxy group 'R6 represents an atom). The trisazo compound or a tautomer thereof, or the salt thereof, according to any one of the above 1 to 4, wherein the trisazo compound represented by the above formula (1) is as follows Formula (5) represents [Chemical Formula 5]

10 201006833 (In the formula (5), the bases A, R丨 to R4 have the same meanings as the formula (丨), and R and R7 have the same meanings as the formula (4), and each of R independently represents a hydrogen atom; C1~.C4 alkoxy. Unsubstituted C1~C4 alkyl; unsubstituted or substituted with sulfoindole - C1~C4 alkoxy; or C1~C4 substituted by sulfo or carboxyl Alkylthio' group; r9 represents a hydrogen atom). The tris-azo compound or a tautomer thereof, or the salt thereof, wherein the group A is a group represented by the following formula (6), [Chemical Formula] 6]

(in equation (6),

Rn to R13 each independently represent a hydrogen atom; a gas atom; a sulfo group; a nitro group; a hydroxyl group; an amine sulfonyl group; a C1 to C4 alkyl group; an unsubstituted or a hydroxy group, an unsubstituted C1 to C4 alkoxy group, a sulfo group or a carboxy-substituted C1 to C4 alkoxy group; or, a C1 to C4 alkylsulfonic acid group h 7) which is unsubstituted or substituted with a hydroxyl group, a sulfo group or a carboxyl group, as in the above 1) to 6) A trisazo compound or a tautomer thereof, or a salt thereof, wherein R1 is a methyl group, R2 is a cyano group or an aminecarbamyl group, R3 is a hydrogen atom, and R4 is a sulfo group. A triazo compound or a tautomer thereof, or a salt thereof, according to any one of the above 1), wherein R5 is a transversely-substituted or decyl-butoxy group, and R6 is hydrogen. Atom H hydrogen atom, methyl or ethyl. 9) The trisazo compound or tautomer thereof according to any one of the above 1) to 8), or a salt thereof, wherein r^r1. Respectively, respectively, are selected from the group consisting of: a hydrogen atom 'chlorine atom; a cross group; an exact group; a methoxy hydrazine propenyloxy group, and a 'renewed hydroxy group substituted' ci~c4 sulphur group. The basis. a diazo compound or a tautomer thereof as described in the above 6), or a salt thereof, wherein R1 is a methyl group, R2 is a cyano group, R3 is a hydrogen atom, R is a sulfo group, and R5 is a sulfonate. The propyloxy group, R6 is a hydrogen atom, R7 is a methyl group, R8 is a propylthio group, R9 is a hydrogen atom, R10 is a methyl group, and two of rU to Ri3 are a sulfo group and one is a hydrogen atom. U) An ink composition comprising at least one of the diazo compounds according to any one of the above 1), or a tautomer thereof, or a salt thereof, as a pigment. 12) An ink jet printing method in which the ink composition as described in (1) above is used as an ink. The ink droplets of the ink are ejected in accordance with a recording signal and adhered to the material to be recorded, thereby performing printing. 13) The inkjet printing method according to the above 12), wherein the above-mentioned material to be recorded in the inkjet printing method is a sheet for information transmission. The inkjet printing method according to the above-mentioned item 13, wherein the sheet for information transmission has a sheet 12 of an ink-absorbing layer containing a porous white inorganic material. The machine is filled with a container containing the ink composition as described in the above 14). 16) A coloring body' which is colored by the diazo compound or a tautomer thereof as described in any one of the above 1) to 1), or a salt thereof. [Effect] The trisazo compound of the present invention or a tautomer thereof, or a salt thereof, has the following characteristics: high solubility in a medium containing water as a main component, and high retention of the compound for a long period of time It is also stable in the case of a concentrated aqueous solution or ink, the concentration of the printed image is very high, and its synthesis is easy and inexpensive. Since the diazo compound of the present invention or a tautomer thereof or the salt thereof is excellent in water solubility, the filter property by the diatomizer in the process of producing the ink composition is good and contains The ink composition or the ruthenium of the compound is prepared from the ink composition. The ink is also excellent in stability or ejection stability at the time of the protection. In other words, the ink composition of the present invention containing the trisazo compound or a tautomer thereof or the salt thereof does not cause solid precipitation, physical property change, color change, etc. after long-term storage, and has good storage stability. Further, the ink composition containing the trisazo compound of the present invention or a tautomer thereof, or a salt thereof is suitable for use in the case of ink jet printing or writing utensils for recording on git paper and ink jet paper. The recording of the recorded image is very high. Even when printing a high-concentration solution, the image does not produce golden floating color, and various fastness, especially 13 201006833 is light resistance and ozone-resistant gas. Excellent in sex. By using in combination with other ink compositions containing magenta, cyan, and yellow pigments, it is possible to perform a full-color inkjet printing which is excellent in various cows and excellent in preservability. Thus, the ink composition 'of the present invention' is extremely useful as a black ink for inkjet printing. [Embodiment] Hereinafter, the present invention will be described in detail. # The azo compound of the present invention or a tautomer thereof, or the like, is a black pigment. The following κ drug von is convenient, including "the compound of the present invention or its tautomeric-azo helmet "Xi Shi. 0 or the salt thereof", which is simply a triazo compound of the present invention. . "The tautomer represented by the above formula (1), except that the 'diazo compound' has a tautomer, and is a compound other than the compound represented by the following formula (7), ... formula (1) It is also included in the ring of the compound represented by the present invention, such as the tautomers to R10, in the following formulas (7) and (8), and the formula (1) Both eyes and the ring of the material of the dotted material have the [chemical formula 7] 3 sense A - N =

[Chemical Formula 8] 14 (7) (8) 201006833

In the above formula (1), 'Ri' represents a carboxyl group, a C1 to C4 alkyl group which is unsubstituted or substituted by a carboxyl group, or a phenyl group which is unsubstituted or substituted with a sulfo group. In the case where R1 in the formula (1) is an unsubstituted Ci~C4 alkyl group, the alkyl group may be either a straight chain or a branched chain, and is preferably a straight chain. Specific examples of the unsubstituted C1 to C4 alkyl group include a straight chain such as a methyl group, an ethyl group, a n-propyl group or a n-butyl group; a mercaptopropyl group, an isobutyl group, a second butyl group, and a third group; Branches such as butyl. In the case where the C1 to C49 base has a county, the base portion of the hospital includes the preferred ones, and the same as above. In the case where R1 is a C1-C4 alkyl group substituted with a carboxyl group, a preferred example thereof is a mercaptomethyl group, a 2-methyl group ethyl group, a 3-methylpropyl group or the like. • Specific examples of the case where R in the formula (丨) is an unsubstituted or sulfo-substituted phenyl group, for example, an unsubstituted phenyl group; a bismuth 2 furnace base, a 4-sulfonate a phenyl group substituted with a sulfo group, such as a phenyl group, a 2,4-disulfophenyl group, a 3 5 disulfophenyl group, or the like, wherein the sulfo group is usually 丨 to 4, preferably 1 to 3, more Good for 1 to 2. Among the above, Ri' in the above formula (1) is preferably an unsubstituted C1 to C4 alkyl group or a substituted phenyl group, and particularly preferably an unsubstituted C1 to C4 alkyl group. 15 201006833 As the formula (1) n-propyl group, the third butyl group is further preferably a methyl group. The specific example of R·1 in the middle is preferably a methyl group, an ethyl group or a stupid group, more preferably a methyl group, a n-propyl group or a stupid group. In the above formula (1), any of R 2 is preferably a group. 0 R represents a cyano group, an amine carbaryl group, or a fluorenyl group. Preferably, it is preferably a cyano group or an amine mercapto group, more preferably a gas.

As a combination of the formula, r2 is a cyano group. (1) A combination of R and R2, preferably R1 is a fluorenyl group or a ruthenium 1 is a methyl group and R2 is an amine fluorenyl group. Better for the former, for: 1) A towel, R3 and R4 each independently represent a hydrogen atom, a gas atomic repeat group, an unsubstituted C1 to C4 alkyl group, or a non-C4 alkoxy group. Where ci is in the formula (1) and r4 is the unsubstituted ci~c4 courtyard base, the '(4) group includes the preferred one and the above R1 is the unsubstituted Cl~C4 alkyl group The situation is the same.

In the case where R3 and R4 in the formula (1) are an unsubstituted C1 to C4 alkoxy group, the alkoxy group may be either a straight chain or a branched chain. Specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, and a third butoxy group. R3 and R4 in the above formula (1) are more preferably a hydrogen atom, a sulfo group or an unsubstituted c 1 to C 4 alkyl group among the above. Specific examples of R3 and R4 in the formula are preferably a hydrogen atom, a base, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a third butyl group, more preferably a hydrogen atom, a contiguous group, or a The group and the isopropyl group are further preferably a hydrogen atom or a sulfo group. 16 201006833 R 3 and 6 in the formula (1) are particularly preferably a hydrogen atom 'methyl group or a contiguous group. The other 3 is preferably a combination of 3 and R 4 . R3 is a gas atom and is a base or R is a sulfhydryl group and R4 is a hydrogen atom. Preferably, the combination of the former. The ring of the above formula (1), the ring substituted by the rule 5 to R7 does not exist in the ring shown by the dotted line. When it is a benzene ring, it is a naphthalene ring in the presence of a ring of a heart. Among them, a ring preferably shown by a dotted line does not exist, that is, a ring which is preferably a heart-substituted ring is a benzene ring.

R to R each independently represent a group selected from the group consisting of: a hydrogen atom; a chlorine atom; a transbasic group; a contiguous group; (4); an amine continuation base; an amine aroma group; An alkyl group; unsubstituted, or a C1 to C4 alkoxy group, a hydroxy C1 to C4 alkoxy group, a sigma group or a sucrose group having a C1 to C4 alkoxy group; Or (d) a mono- or di-C1~C4-andylamino group substituted with a carboxy group; a carboxy group; an unsubstituted or substituted C1~C4 alkylcarbonylamino group substituted by a hydroxy or a carboxy group; unsubstituted or via a hydroxy group, Sulfhydryl or fluorenyl substituted n, _ci~c4 alkylureido; unsubstituted, or a stupid ring, a non-substituted hydrazine-C4 alkyl, nitro, sulfo, or carboxy substituted benzene Alkyl; unsubstituted, or phenyl ring via a gas atom, unsubstituted c丨~C4 alkyl, nitro, sulfo, or carboxy substituted benzyl alcohol amine; and, unsubstituted, or A phenyl ring is substituted with a gas atom, an unsubstituted c 1 to C 4 alkyl group, a nitro group, a sulfo group, or a carboxyl group substituted with a phenylsulfonylamino group / R to R is an unsubstituted C1 When the case ¢ 4 alkyl group, the alkyl group is a straight chain, branched chain, any one of which may be of, preferably straight-chain. Specific examples of the unsubstituted C1 to C4 entertainment include a methyl group, an ethyl group 17 201006833, a straight chain such as a n-propyl group or a n-butyl group; an isopropyl group, an isobutyl group, and a second butyl group; Branches such as the third butyl group. A preferred specific example is a methyl group or an ethyl group, more preferably a methyl group. In the case where 11 to R of the formula (1)_ is an unsubstituted C1 to C4 alkoxy group, the silk group includes the preferred (four), and the above R4 is an unsubstituted C1 to C4 alkoxy group. The same can be. Φ Φ In the case where the oxy group of the compound is substituted with (4), unsubstituted CM to C4 silk group, or substituted with a base CM to C4 alkoxy group, a base group or a slow group, examples thereof include, for example, 2 Alkyloxy, 2-propenyloxy, 3-propenyloxy, etc. via a C1~C4 alkoxy group; methoxyethoxy, ethoxyethoxy, n-propoxy Oxyl, isopropoxyethoxy, n-butoxyethoxyoxypropyloxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propyl Oxybutoxy group and the like unsubstituted C1~C4 alkoxy group CI~C4 alkoxy; 2·(tetra)ethoxyethoxy(tetra)yl C1~C4 alkoxy C1~C4 methoxyl; 3_continued A propyl group such as a propyloxy group or a hexyloxy group; a thiol group having a mercapto group such as a thiol group; a thioloxy group; a carboxypropyloxy group; In the case where my in the formula (1) is an unsubstituted mono or an alkyl group, the C1 to C4 (d) moiety may be either a straight bond or a bond. Specific examples thereof include a methylamino group, an ethylamino group, a n-propylamino group, an isopropylamine group, a n-butylamino group, a dif-amino group, a diethylamino group, a di-n-propylamino group, a di-n-butylamino group, and the like. A straight bond; a branched chain such as a second butylamine group, a third butylamino group or a diisopropylamine group. When the mono- or di-C1-C4 alkylamino group is substituted by a hydroxysulfo group or a carboxy group, 'as a specific example thereof', for example, 2: hydroxyethyl group 18 201006833 amine group, 2-hydroxypropylamino group, a mono- or di-C1-C4 alkylamino group substituted by a hydroxy group such as 2,2,-dihydroxydiethylamine; 2-sulfoethylamino, 3-sulfopropylamino, 4-sulfobutylamino, a mono- or di-C1-C4 alkylamino group substituted with a sulfo group such as 3,3'-disulfodipropylamino; carboxymethylamino, 2-carboxyethylamino, 3-carboxypropylamino, 2,2' a mono- or di-C1-C4 alkylamino group substituted by a carboxyl group such as a dicarboxydiethylamine group. In the case where R5 to R7 in the formula (1) are an unsubstituted C1 to C4 alkylcarbonyl group, the C1 to C4 alkyl moiety may be either linear or branched. For the straight chain. Specific examples thereof include an ethyl hydrazino group, a propyl fluorenyl group, a butyl hydrazino group, and the like. In the case where the C1 to C4 alkylcarbonylamino group is substituted with a hydroxyl group or a carboxyl group, specific examples of the C 1 to C 4 alkylcarbonylamino group include, for example, a mercaptoamine group and a 2-hydroxypropane group. a carboxy-C1 to C4 alkylcarbonylamino group such as a fluorenylamino group, a 4-pyridylamino group or the like, a C1 to C4 alkylcarbonylamino group, a 3-carboxypropylamino group or the like. In the case where R5 to R7 in the formula (1) are N'-Cl~C4 alkylureido groups, it is preferred to have a substituent as compared with the unsubstituted. In the case where the N'-Cl~C4 alkyl group is substituted with a thiol group, a contiguous group, or a succinyl group, as a specific example thereof, for example, N, _2-transethylethyl gland group, N-3 - via the base ethyl gland group, such as Ν'-transcarbyl C1~C4 ureidourea; N,-2-exidylethylglycosyl, Ν'-3-contigylpropylglycine, etc. Ci~C4 ureido; N,-carboxy guanylureido, N,-2-carboxyethylureido, N, _3_carboxypropylureido, hydrazine, ·4·carboxybutylureido, etc. N , -carboxyl 〇~(:4 alkylureido group, etc. R5 to R7 in the formula (1) are a phenylamino group, a benzoylamino group having a substituent of 19 201006833, respectively, or When the substituent of the benzene ring contained in each group is a C1 to C4 alkyl group, the alkyl group may be any of a straight chain, a branched chain, or a cyclic group. It is preferably a straight chain or a branched chain. Specific examples thereof include a straight chain such as a mercapto group, an ethyl group, a n-propyl group, and a n-butyl group; and an isopropyl group, an isobutyl group, a second butyl group, and a third group. A butyl group or the like. In the formula (R5 to R7 in D is unsubstituted or a benzene ring through a gas atom) In the case of an unsubstituted C1-C4 alkyl group, a nitro group, a sulfo group or a phenylamino group substituted with a buffer group, examples thereof include, for example, an unsubstituted phenylamine group, or 2 a phenylamino group substituted with a gas atom such as a chlorophenylamino group, a 4-phenylphenylamino group, a dioxin group, or a 2-dimethylphenylamino group; a 4-phenylbutylamino group such as an unsubstituted hydrazine-C4 alkyl substituted phenylamine group; a 2-nitrophenylamino group, a 4-nitrophenylamino group or the like substituted by a nitro group; Benzylamino group; 3-sulfophenylamino group, 4-sulfophenylamino group, 2,4·disulfophenylamino group, 3,5-disulfophenylamino group, etc. Substituted phenylamino group; 2-carboxylamino group, 4-carboxyphenylamino group, 2'5-carboxyphenylamino group, 3,5-dicarboxyphenylamino group, etc. Alkyl group, etc. R5 to R7 in the formula (1) are unsubstituted or a stupid ring gas atom, unsubstituted C1 to C4 alkyl group, nitro group, sulfo group, or carboxyl group substituted benzoate In the case of an amine group, as a specific example, for example, unsubstituted A benzoylamino group substituted by a gas atom such as a benzoylamino group or a 2-gas benzoylamino group, a 4-benzophenanthrylamino group or a 2,4-dichlorophenylamino group. , 2-methylbenzoinylamino, 3-methylbenzhydrylamino, 4-methylbenzyl 20 201006833 mercaptoamine-substituted benzhydrylamino group substituted by Cl~C4 alkyl a nitro-substituted benzhydrylamino group such as a 2-nitrophenylamino group, a 4-nitrobenzhydrylamino group, a 3,5-dinitrobenzimidylamino group; a sulfo group-substituted phenylhydrazino group such as a sulfobenzoylamino group or a 4-sulfobenzylamino group; a 2-carboxybenzylideneamino group, a 4-carboxybenzylidene group An alkaloid, a 3,5-dicarboxybenzoylamino group or the like which is substituted by a thiol group. In the case where R5 to R7 in the formula (1) are unsubstituted or a phenyl ring is substituted by a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a carboxyl group substituted phenylsulfonylamino group. In the case of the specific example, for example, an unsubstituted sulfhydryl sulfhydryl group or a 2-phenylphenylsulfonic acid amine group or a 4-phenylphenylsulfonic acid amine group may be substituted by a gas atom. Phenylsulfonic acid amino group; 2 methylphenylsulfonylamino group, 4-nonylphenylsulfonylamino group, 4_t-butylphenylsulfonylamino group, etc. via C1~C4 Alkyl-substituted phenylsulfonylamino; 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, "nitrophenylsulfonylamino", etc. Substituted phenylsulfonylamino; 3-sulfophenylsulfonylamino, 4-sulfophenylsulfonylamino, etc. A phenyl-decylamino group such as a phenyl-carboxylamino group or a 4-sulfophenylphosphonic acid-based amine group, etc., wherein a specific example of R5 to R7 in the formula (1) is preferably: Hydrogen atom, carboxyl group, sulfo group, sulfhydryl group, ethyl group, decyloxy group, ethoxy group, 2-hydroxyl group Oxyl, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, methylamino, ethylamino, 2-hydroxy Amino, 2-sulfoethylamino, 3-thylpropylamino, 2- ketoethyl, dimethylamino, diethylamino, 2,2'-dihydroxydiethylamine, 2 , 2,-dicarboxydiethylamino, 3,3,_2 21 201006833 canister dipropylamino, ethyl arylamino, 3-mercaptopropylamino, 4-hydroxybutanylamine, Ν' -carboxy-mercaptoureido, sulfoethylureido, 4-retentylphenylamino, 2,4-disulfophenylamino, 2,5-dicarboxyphenylamino,

Benzoylamino, 3-sulfobenzylidenylamine, 2-carboxybenzylidenylamine, phenylsulfonylamino, 4-methylphenylsulfonylamino, 4_ More preferably: a nitrophenylsulfonylamino group, a 3-sulfophenylsulfonylamino group, a 4-carboxyphenylsulfonylamino group, or the like, more preferably a hydrogen atom, a sulfo group, a methyl group or a decyloxy group. , 2-hydroxyethoxy, 2-akisylethoxy, 3-Mexylpropoxy, 4-desylbutoxy, monomethylamino, 3,3·-disulfodipropylamino, B Merylamino, 3-carboxypropenylamine, N'-2-sulfoethylureido, 2,4-disulfophenylamino, benzoquinoneamino, 4-methylbenzene The sulfonylamino group is further preferably a hydrogen atom, a sulfo group, a methyl group, a methoxy group or a 3-sulfopropoxy group. The preferred combination of R5 to R7 in the formula (1) is not the same when the substituted ring is a benzene ring and the substituted ring is a naphthalene ring. When the ring substituted by R5 to R7 is a naphthalene ring, the combination of the rule 5 to r7 is preferably a combination of any two of which is a hydrogen atom and the other one is a sulfo group. The position of the sulfo group is not particularly limited, but the position of substitution of the primary nitrogen group in combination with the benzoindole ring is. When the substitution position of the substituted nitrogen group of the substituted ring is 4, it is preferred that the contig is substituted for the 7 position. When the ring substituted by R7 is a benzene ring, it is preferred that A is a contigyloxy group or a contigyl butoxy group, more preferably a 3 _ cis propyloxy group "4• contigyl butyloxy group' Further, a tetra-34-propoxy group; a hydrogen atom; and r7 is a hydrogen atom methyl group or ethyl group is more preferably a mercapto group. The ring of ', the ring in the above formula (1), R8 to R10 replaced by 22 201006833, the ring shown does not exist, represents a benzene ring, and the ring shown by the dotted line represents a naphthalene ring, of which The ring shown by the dotted line does not exist, that is, it is preferred that the ring substituted by R8 to R1G is a benzene ring. R8 to R1G each independently represent a group selected from the group consisting of a hydrogen atom; a gas atom; a hydroxyl group; a sulfo group; a carboxyl group; an aminesulfonyl group; an amine carbenyl group; and an unsubstituted C1 to C4 alkyl group. a C1 to C4 alkoxy group which is unsubstituted or substituted with a thiol group, a C1 to C4 alkoxy group, a hydroxy C1 to C4 alkoxy 'sulfo group, or a carboxyl group φ; substituted by a hydroxyl group, a sulfo group or a carboxyl group; a C1 to C4 sulfur-burning group; an unsubstituted or mono- or di-C1 to C4 alkylamino group substituted by a benzyl group, a cis group or a slow group; unsubstituted or substituted by a base or a slow group C1~ a C4 alkyl group; an unsubstituted or N,-C1~C4 alkylureido group substituted by a benzyl group, a contiguous group or a carboxy group; unsubstituted or a benzene ring via a gas atom, unsubstituted a C1 to C4 alkyl group, a nitro group, a hydroxy group, or a thiol group substituted with a phenyl group; an unsubstituted ' or a benzene ring via a chlorine atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, Or a carboxy-substituted alum-based fluorenylamino group; and, unsubstituted, or a stupid ring via a chlorine atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group Substituted phenylsulfonylamino group In the case where R8 to R1G are an unsubstituted C1 to C4 alkyl group, the alkyl group may be any of a straight chain and a branched chain, and is preferably a straight chain. Specific examples of the unsubstituted C1 to C4 alkyl group include a linear group such as a mercapto group, an ethyl group, a n-propyl group, and a n-butyl group; and an isopropyl group, an isobutyl group, and a second butyl group. Base and other branches. A preferred specific example is a methyl group or an ethyl group, more preferably a methyl group. In the case where R8 to Rio in the formula (1) are unsubstituted C1 to C4 alkoxy 23 201006833, the alkoxy group preferably includes the above-mentioned R3 and oxime unsubstituted C1 to C4. The alkoxy group can be the same. * When the alkoxy group is substituted with a trans group, an unsubstituted ... / a sulfhydryl group, a hydroxy C1 - C4 alkoxy group, a sulfo group, or a carboxyl group, as a specific example thereof, for example, 2_ a hydroxy-C1~C4 alkyl fluorenyl group such as a ethoxy group, a 2-hydroxyloxy group, a propyloxy group, a methoxyethyl group, an ethoxyethoxy group, a n-propoxy ethoxy group, or a different Propoxyethoxy n-butoxy

Ethoxylated, alkoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, etc. a C1 to C4 alkoxy group; a hydroxy C1 to C4 alkoxy group C1 to C4 alkoxy group such as a 2-hydroxyethoxyethoxy group; a sulfo group such as a 3-sulfopropoxy group or a 4-sulfobutoxy group; C1 to C4 alkoxy group; carboxymethoxy group, 2-carboxyl ethoxy group, % decylpropoxy group and the like. In the case where R8 to R10 in the formula (1) are an unsubstituted C1 to C4 alkylthio group, the C1 to C4 alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include, for example, a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, a dimethylthio group, a diethylthio group, a di-n-propylthio group, and a di-n-butyl group. a straight chain such as a butylthio group; a branched chain such as a second butylthio group, a third butylthio group or a diisopropylthio group; and the like. In the case where the thio group is substituted by a hydroxyl group, a sulfo group or a carboxyl group, as a specific example thereof, for example, 2-hydroxyethylthio group, 2-hydroxypropylthio group, 2,2'-diyl group II may be mentioned. a thiol-substituted cl~c4 alkylthio group such as an ethylthio group; a 2-hydroxyethylthio group, a 3-sulfopropylthio group, a 4-sulfobutylthio group, and a 3,3'-disulfodipropylthio group. a C1~C4 alkylthio group substituted by a sulfo group; a carboxymethylthio group, 24 201006833 2-rethylthio group, 3-sulfopropylthio group, 2,2'-di-sulfanyldiethylthio group, etc. The number of such substituents is not particularly limited, but is usually from 1 to 3, preferably from 1 to 2, more preferably 1, to the carboxyl group-substituted C1 to C4 alkylthio group. In the case where R8 to R10 in the formula (1) are an unsubstituted mono- or di-Ci-C4 alkylamino group, the C1-C4 alkyl moiety may be either a straight chain or a branched chain. Specific examples thereof include amidino group, ethylamino group, -n-propylamino group, isopropylamino group, n-butylamino group, dimethylamino group, diethylamino group, φ di-n-propylamino group, and di-n-butylamine. A straight chain such as a base; a branched chain such as a second butylamine group, a third butylamine group or a diisopropylamine group. In the case where the mono- or di-C1-C4 alkylamino group is substituted by a hydroxyl group, a sulfo group or a carboxyl group, 'for specific examples thereof, for example, 2-hydroxyethylamino group, 2-hydroxypropylamino group, 2, 2 a mono- or di-C1-C4 alkylamino group substituted by a hydroxy group such as '-dihydroxydiethylamino group; 2-sulfoethylamino group, 3-sulfopropylamino group, 4-sulfobutylamino group, 3,3 a mono- or di-C1~C4 alkylamino group substituted with a sulfo group such as '-disulfodipropylamino group; a sulfhydrylamino group, a 2-sulfoethylamino group, a 3-rebase 1,3-propylamine group, 2,2 a mono- or di-C1~C4 alkylamino group substituted by a carboxyl group such as a 'dicarboxydiethylamino group. In the case where R8 to R10 in the formula (1) are an unsubstituted C1 to C4 alkylcarbonylamino group, the C1 to C4 alkyl moiety may be either a straight chain or a branched chain, preferably straight. Chain. Specific examples thereof include an ethyl amide group, a propyl fluorenyl group, and a butyl hydrazino group. In the case where the C1 to C4 alkylcarbonylamino group is substituted by a hydroxyl group or a carboxyl group, 'specific examples of the C1 to C4 alkylcarbonylamino group include, for example, hydroxyethylamino group and 2-hydroxypropyl fluorenyl group. Amino group, 4-hydroxybutanylamino group 25 201006833 and the like hydroxyCl~C4 alkylcarbonylamino group; 3-carboxyl propylamino group and the like carboxyl group C1 to C4 alkylcarbonylamino group and the like. In the case where R8 to R10 in the formula (1) are Ν'-Cl~C4 alkylureido groups, it is preferred to have a substituent as compared with the unsubstituted. In the case where the N'-Cl~C4 alkylureido group is substituted with a hydroxyl group, a sulfo group or a carboxyl group, examples thereof include, for example, n, -2-transethylethyl group, N'-3 -N-hydroxyl-C1~C4 alkylurea group such as hydroxyethylurea; N,_2_ 确 乙基 乙 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基N-carboxyl-ureido, N-carboxy-mercaptoureido, n'-2-carboxyethylureido, N,_3-carboxypropylureido, N,-4-carboxybutylureido, etc. N,-carboxy*C1 ~C4 alkylurea group and the like. R8 to R1G in the formula (1) are a phenylamino group, a benzhydrylamino group or a phenylsulfonylamino group which have a substituent in the following order, and the benzene contained in each group When the substituent of the ring is a C1 to C4 alkyl group, the alkyl group may be any of a straight chain, a branched chain, or a cyclic group, and is preferably a straight chain or a branched bond. Specific examples thereof include a straight chain such as a methyl group, an ethyl group, a "n-propyl group or a n-butyl group", and a branched group such as an isopropyl group, an isobutyl group, a second butyl group or a tributyl group. When R8 to Rig in the formula (1) are unsubstituted or a phenylamine group in which a benzene ring is substituted with a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a carboxyl group, Specific examples thereof include, for example, an unsubstituted styrylamino group or a 2-phenylphenylamino group, a 4-chlorophenylamino group or a 2,4-diphenylamino group substituted by a gas atom. a phenylamine group; a 2-phenylphenylamine group; a 4-methylphenylamino group; a 41-butylphenylamino group; an unsubstituted phenyl group substituted with a C4 group; 2n benzene Base, μ-phenyl phenyl 26 201006833 Amine-substituted nitro-substituted phenylamine; 3-sulfophenylamino, 4-phenylphenylamino, 2,4-disulfophenylamine Phenylamino group substituted by a group such as a 3,5-disulfophenylamino group; 2-t-phenylphenylamino group, 4-nonylphenylamino group, 2,5-di-co-phenylbenzene A phenylamino group substituted with a few groups such as a arylamino group, a 3,5-di-redomylphenylamino group or the like. R8~R1G in the formula (1) is an unsubstituted or phenyl ring via a gas atom, an unsubstituted C1 to C4 alkyl group, an exact group, an exact group, or a substituent substituted by a base group. In the case, 'for specific examples thereof, for example, unsubstituted benzhydrylamino group' or 2-epoxybenzhydrylamino group, 4-ephenylamino group, 2,4-·1 a benzylamino group substituted by a chlorine atom such as a wind-based amino group; a 2-methylbenzhydrylamino group, a 3-mercaptophenylhydrazino group, a 4-mercaptobenzamide group a benzoylamino group substituted by a C1 to C4 alkyl group; a 2 nitrobenzoylamino group, a 4-nitrophenyl fluorenylamino group, a 3,5-dinitro azinoylamino group a nitro-substituted benzhydrylamino group; a 2-sulfobenzylamino group, a 4-sulfobenzylamino group, a sulfo-substituted benzoylamino group; ^ 2- A carboxyl group-substituted benzoylamino group such as a carboxybenzylideneamino group, a 4-carboxybenzylamino group, or a 3,5-dicarboxybenzene-methylamino group. In the case where R8 to R1G in the formula (1) are unsubstituted or a phenyl ring is substituted with a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group or a carboxyl group substituted phenylsulfonylamino group. In a specific example, for example, an unsubstituted phenylsulfonylamino group, or a 2-phenylphenylsulfonylamino group or a 'p-phenylsulfonylamino group, which is substituted by a gas atom, may be mentioned. Phenylsulfonylamino group; nonylphenylsulfonic acid amine group, 4-methylphenylsulfonylamino group, 4th butylphenylsulfonylamino group, etc. substituted by C1 to C4 alkyl group Stupid sulfonylamine 27 201006833 base; 2-nitrophenylsulfonylamino, 3-nitrophenylsulfonylamino, 4-nitrophenylsulfonylamino, etc. Substituted phenylsulfonylamino group; 3-sulfophenylsulfonylamino group, 4-sulfophenylsulfonylamino group, sulfo group-substituted phenylsulfonylamino group; 3-carboxyl group a phenylsulfonylamino group substituted with a carboxyl group such as a phenylsulfonylamino group or a 4-carboxyphenylsulfonylamino group. Specific examples of R8 to R1G in the formula (1) are preferably a hydrogen atom, a carboxyl group, a sulfo group, a methyl group, an ethyl group, a f-oxy group, an ethoxy group, a 2-hydroxyethoxy group, or a 2-dimer. Ethyl ethyl lactide, 3-n-propoxypropoxy, 4-th-butyloxy, 3-decylpropylthio or 4-sulfobutylthio, carboxymethoxy, 2-carboxyethoxy, hydrazine Amino, ethylamino, 2-hydroxyethylamino, 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino, dimethylamino, diethylamino, 2, 2' -dihydroxydiethylamino, 2,2'-dicarboxydiethylamino, 3,3'-disulfodipropylamino, ethylamino, 3-carboxypropylamino, 4-hydroxyl Butylated amino group, Ν'-carboxymethyl glyphosyl, Ν'-2-thanoyl yl group, 4-cenylphenylamino group, 2,4-disulfophenylamino group, 2,5- Dicarboxyphenylamino, benzhydrylamino, 3-Φ sulfobenzylideneamino, 2-carboxybenzylideneamino, phenylsulfonylamine, benzyl, 4-methylbenzene a sulfonylamino group, a 4-nitrophenylsulfonylamino group, a 3-sulfophenylsulfonylamino group, a 4-carboxyphenylsulfonylamino group, etc., more preferably: a hydrogen atom, Gas atom, sulfo group Sulfhydryl, decyloxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, diammonium, 3,3'-disulfonate Dipropylaminopropyl, ethinylamino, 3-carboxypropylamino, Ν'-2-sulfoethylureido, 2,4-disulfophenylamino, phenylhydrazine Further, 4-methylphenylsulfonylamino group is more preferably a hydrogen atom, a sulfo group, a methyl group, a decyloxy group or a 3-sulfopropoxy group. 28 201006833 The preferred combination of R8 to 丨0 炎 ## to 11 in formula (1) is not the same when the substituted ring of the 8th generation is a naphthalene ring. When the ring substituted by R to R10 is a tower Q mannane core, the combination thereof is preferably R8 is a hydrogen atom, R is a sulfopropoxy group, RU) is a θ 〇8 ηη von von terminus, or R8 is Any two of them are hydrogen atoms and the rest - .^ ^ ^ are sulfo groups. The position of each substituent is not particularly limited, and the substitution position of the azo group in the combination of Y 曰 斑 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A When the position is 1 bit,

Preferably, the former is substituted by R9 for 5, 7/R for 7, and the latter for 7. R8 to R1. When the substituted ring is a benzene ring, it is preferably: R, a resopropyloxy group, a contiguous T oxy group, a 4-ylpropylthio group or a benzyl thio group. More preferably, it is a hydroxypropyl group or a W group.懿 懿; R 9 is a hydrogen atom; R 1 (U methyl or ethyl, more preferably methyl. The position of each substituent is not particularly limited, but when the position of the azo group bonded to the group A is 4 positions and When the substitution position of the azo group bonded to the ring substituted with R7 is a ruthenium, it is preferred that r8 is substituted at the 2-position and r1q is substituted at the 5-position. The group A in the formula (1) is unsubstituted or has a benzothiazolyl group; a thiadiazolyl group; or a thiazolyl group. When the benzothiazolyl group has a substituent, it may have a group selected from a gas atom; a sulfo group; a nitro group; a hydroxyl group; Unsubstituted C1~C4 alkyl; unsubstituted, or C1-C4 alkoxy substituted by hydroxy, C1-C4 alkoxy, sulfo, or carboxy; unsubstituted, or via hydroxy, sulfo Or a carboxy-substituted C1~C4 alkylsulfonyl group; and not 29 201006833 substituted 'or a benzene ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a Shikizaki, or a ruthenium The substituents in the group consisting of the substituted phenyl fluorenyl groups may be the same as those of R5 to R8 in the above formula (1), including the equivalent and the preferred ones. The number of the substituent is not particularly limited, but is usually 1 to 4, preferably 1 to 3, more preferably 2. The above is preferably a sulfo group. The thiadiazolyl or thiazolyl group has a substituent. In a case, it may have a gas selected from the group consisting of: a gas atom; a sulfhydryl group; a fluorenyl group; a hydrazine group; an amine base; a sulfhydryl group; and, unsubstituted, or a hydroxyl group, a C1 to C4 alkoxy group, a hydroxyl group C1 C4. a substituent in the group consisting of ci or a sulfur-substituted group substituted with a thiol group or a sulfo group. The number of substituents is not particularly limited, but is preferably 1. The above preferred thiol group; or, (iv) group The hydroxyl group is substituted with a C1~C4 alkylthio group. Further preferably, it is a sulfo group, a sulfopropylthio group or a carboxymethylthio group.

The compound represented by the above formula (1) is preferably a compound represented by the above formula (2). In the formula (2), the ring ’, 至 R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R The compound represented by the above formula (3), preferably a compound represented by the above formula (2), is preferred. In the formula (3), the bases A and Ri to R10 may be the same as the above formula (1). Preferably, the bases A, ... to r4 of the above formula (4) are included. A compound represented by the compound represented by the above formula (3). In the above formula (4), the preferred ones are the same as the above formula (丨) 201006833 R5 and R7 each independently represent a hydrogen atom; a sulfo group c丨~C4 alkoxy group; an unsubstituted C1 to C4 alkyl group; a hydroxy group; or an unsubstituted or c 1 to C 4 alkoxy group substituted by a base; R 6 represents a hydrogen atom. R5 and R7' in the formula (4) are preferably the same as those in the above formula (R5 and R7 in the formula). The compound represented by the above formula (4) is preferably the above. In the above formula (5), the group A, R1 to R4, R5 to R7, ❹, preferably the same as the above formula (1), etc. R to RW. Respectively represent a hydrogen atom; a sulfo C1 to C4 alkoxy group; an unsubstituted C1 to C4 alkyl group; a hydroxyl group; an unsubstituted or a C1 to C4 alkoxy group substituted by a hydroxyl group; or, a sulfo group or a carboxyl group-substituted Cl~c4 sulphur group; r6 represents a hydrogen atom. R8 to R^' in the formula (5) includes, preferably, the same as R and R10 in the above formula (1) In the above formulas (1) to (5), the group A is preferably a group represented by the above formula (6). In the above formula (6), R" to Rn are independently represented. Hydrogen atom; gas atom, sulfo group; nitro group; hydroxyl group; amine sulfonyl group; unsubstituted or C1 to C4 alkoxy group substituted by hydroxy group, unsubstituted C1~C4 alkoxy group, sulfo group or carboxyl group Or unsubstituted Or a C1~C4 alkylsulfonyl group substituted by a hydroxy group, a sulfo group or a carboxyl group. Rh to Rn in the formula (6) is unsubstituted or hydroxy, unreacted, Cl~C4 decyloxy, When the base or the slow group is substituted with Ci~c4, the alkoxy group, including the preferred one, is equivalent to the above formula (C 1 to C 4 alkoxy groups in R 5 to R 7 in u 31 201006833) The same can be.

In the case where Rn to R13 in the formula (6) are a C1 to C4 alkyl group which is unsubstituted or substituted with a hydroxyl group, a sulfo group or a carboxyl group, as a specific example, it may be exemplified by: methylsulfonate a straight or branched bond such as an ethyl sulfonyl group, a propyl sulfonyl group, an isopropyl aryl group, a n-butyl fluorenyl group, a second butyl fluorenyl group, a third butyl fluorenyl group, or the like Substituted ~C4 Institute based sulfonyl alcohol; 2-hydroxyhexylsulfonyl, 3-hydroxypropylsulfonyl and other hydroxy C1 ~ C4 alkyl base; 2-sulfopropyl decyl, 3 a sulfo ci~C4 alkylsulfonyl group such as a propyl group or a 4-sulfobutylsulfonyl group; a carboxymethyl group, a 2-carboxyethylsulfonyl group, a 3-carboxypropylsulfonyl group Mercapto group and the like carboxy oxime ~ C4 alkyl sulfonyl group and the like. Specific examples of Ri丨 to Rn in the formula (6) are preferably a hydrogen atom, a gas atom, a sulfo group, a nitro group, a f-oxy group, an ethoxy group, a hydrazine hydroxyethoxy group, or a 2-sulfoethoxy group. , 3-sulfopropoxy, 4-sulfobutoxy, carboxydecyloxy, 2-repentylethoxy, methyl benzyl, ethyl decyl, tert-butyl styrene , 2-hydroxyethylsulfonyl, 3'-propenylsulfonyl, 2-hydrazinoethylsulfonyl, phenylsulfonyl, 4-phenylphenylsulfonyl, "phenyl Sulfonic acid, 2,4-dimethylphenyl continuation, 4,ylphenyl fluorenyl, 4-thyl phenyl mercapto, 2, phenyl(tetra)yl, phenyl phenyl cation, The gas atom, the stilbene group, the methoxy group, and the methyl group are further preferably a hydrogen atom, a methoxy group, or a decyl propoxy group. Preferably, at least one of Rn is a nitrogen atom, and preferably at least one is a substituent other than a ruthenium atom. The combination of Rn to R13 in the formula (6) is preferably one having a sulfo group and 32 being a hydrogen atom, or two being a sulfo group and the other being a hydrogen atom, more preferably a combination of the latter. The position of substitution of the sulfo group on the benzoxazole ring is not particularly limited. Preferably, the former is 6 and the latter is 4 and 6. More preferably, the compound formed by combining the preferred substituents of the above formula (丨) to (6) is preferably a compound which is preferably combined with each other. The same is true for the others. Further, as described above, in the formulae (7) to (8), the ring substituted by the base group and R1 to R10, including the ring shown by the broken line, has the same meaning as in the above formula (1). Further, it is preferably the same as in the above formula (1) in terms of a preferred combination, a preferred combination of the other, and the like.

Φ 201006833 The salt of the trisazo compound represented by the above formula (1) is an inorganic or organic cation H, as a specific example salt of the inorganic salt - the soil test metal salt, and the recorded salt, preferably inorganic #, Salt and salt. Further, the salt of the organic cation is, for example, a tetra-order ion represented by the following formula (9), but is not limited thereto. Further, it may be a mixture of Youcheng, its tautomers, and various salts thereof. For example, a mixture of a sodium salt and a π π mixture, a mixture of a free acid and a sodium salt, a lithium salt, a sodium salt, a mixture of fentan and a sulfonium salt, or the like can be used. According to the type of salt, there is also a case where the solubility is not sufficient, and it is also possible to obtain a salt containing a plurality of salts, etc., by appropriately selecting the salt when necessary. a mixture of physical properties. [Chemical Formula 9] m 33 201006833

In the formula (9), 'z1, Z2, Z3 and Z4 each independently represent a group selected from the group consisting of: a chlorine atom, a group, a transalkyl group, and a hydroxyalkoxyalkyl group. Specific examples of the alkyl group of Z1, Z2, Z3 and Z4 in the formula (9) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a first butyl group. Base, third butyl, etc. Specific examples of the hydroxyalkyl group include a methyl group via a methyl group, a 3-propyl group, a 2-propyl group, a 4-butyl group, a 3-hydroxy group, and a 2-hydroxy group. A hydroxy group such as butyl C1 to C4 alkyl. Examples of the hydroxyalkoxyalkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, a 3-hydroxyethoxypropyl group, a 2-hydroxyethoxypropyl group, and a 4-hydroxyl group. a hydroxy C1 - C4 alkoxy C1 - C4 alkyl group such as oxybutyl, 3-hydroxyethoxybutyl or 2 hydroxyethoxybutyl, preferably hydroxyethoxy hydrazine C1 to C4 Burning base. As a particularly preferred one, a hydrogen atom; a methyl group; a methyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and 2_ Hydroxyalkyl group such as hydroxybutyl group; hydroxyethoxymethyl group, 2-hydric ethoxyethyl group, 3-hydroxypropyl propyl group, (tetra)ethoxypropyl group 4 ethoxylated butyl group And a hydroxyethoxy C1 to C4 alkyl group such as a transyloxybutyl group or a 2-phenylethoxybutyl group. Specific examples of the combination of zl, z2, & and z4 of the preferred compound of the formula (9) are shown in the following Tables. [Table 1] 34 201006833 Compound No. Z1 Ζ2 Z3 Z4 1-1 Η CH3 CH3 CH3 1-2 CH3 CH3 CH3 CH3 1-3 Η -C2H40H -C2H40H -C2H40H 1-4 CH3 -C2H40H -C2H40H -C2H40H 1-5 Η -CH2CH(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 1-6 CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 -CH2CH(OH)CH3 1-7 Η -C2H40H H -C2H40H 1-8 CH3 -C2H40H H -C2H40H 1-9 Η -CH2CH(OH)CH3 H -CH2CH(OH)CH3 1-10 CH3 CH2CH(OH)CH3 H -CH2CH(OH)CH3 1-11 CH3 -C2H40H CH3 - C2H40H 1-12 CH3 *CH2CH(OH)CH3 CH3 -CH2CH(OH)CH3 The trisazo compound represented by the above formula (1) can be synthesized, for example, by the method described below. Further, for the sake of convenience, the acidic functional groups of the compounds in the respective steps are represented by the form of the free acid. Further, in the following formulas (10) to (15), the respective rings ' substituted by η, a group A, R1 to R10, and R5 to R10 include rings represented by broken lines, each having the above formula (1) The meaning of the same summer. • The compound represented by the following formula (10) is diazotized by a usual method, and then subjected to a coupling reaction with a compound represented by the following formula (11) by a usual method to obtain a formula (12) ) the compound shown. Further, the compound represented by the formula (10) can be synthesized in accordance with the method described in Patent Document 1A. Further, the compounds represented by the following formulas (11) and (13) can be synthesized by a usual method. Further, the compound represented by the formula (10) can also be synthesized by a usual method. 35 201006833 [chemical formula ίο] A-nh2 (10) [chemical formula]

(11) [Chemical Formula 12] R8

(12) The obtained compound represented by the formula (12) is diazotized by a usual method, and then subjected to a coupling reaction with a compound represented by the following formula (13) by a usual method to obtain A compound represented by the following formula (14). [Chemical Formula 13] R5

’, (13) [Chemical Formula 14] 36 (14) (14) 201006833

The obtained compound represented by the formula (14) is diazotized by a usual method, and then subjected to a coupling reaction with a compound represented by the following formula (15) by a usual method, whereby The di-halogen compound of the present invention represented by the above formula (〇) [Chemical Formula 15]

Further, the compound represented by the above formula (15) can be synthesized in accordance with the method described in Patent Document 5. The compound of the present invention represented by the above formula (1) is not particularly limited, and examples thereof include compounds represented by the structural formulae shown in the following Tables 2 to 5. In the respective tables, 'for convenience, a functional group such as a sulfo group or a carboxyl group is described as a free acid. 37 201006833 [Table 2]

Compound No, Structural Formula 1 S03H /S〇3M o-/7CN H〇3S^^N=N^N=N^N=NH& h5c ho, s〇3H 2 so3h 1°^ S—/0-^» ^ CN HO3S^^'NaN'0KN::N'*0"NeN~&i h3c h^c ho Vs% ,so3h 3 SOaH /SC^H ?^Η O-/-^ O-^i^C CN h〇^J^]Hn=n-^-n=n-0~n=n-^n H^/ h^C HO y5^ SO^H 4 SOaH .SOaH O^HgCJCN HO3SX^S^N= N"^NSN^0'N=N>ibi h3c h3c ho 'SOaH 5 SC^H 〇丨 广 - Guang Shao! °3H 0-^ h3c comh2 H. Force: Bu (four) points = N to make H3C HsC ho 'SOsH 6 SOjH .SOaH 〇_yf p-/~H3C^ jSOHHz Η(3ίδ〇Ν=Ν·0·Ν=Ν·0~Ν=ι^^ h3c h3c Ho V5^, so3h 38 201006833 [Table 3]

Compound No, Structural Formula 7 SO,H _ 0-^ h3g conh2 hosSJCO~N=N_H0~N=N~0^_*^^ HaC HaC HO, so# 8 sojH /5°^ f03*1 S-^f 〇^HaC C〇NH2 K3C h^cmy^| 'so# 9 JSO^H /O3H fC^H O-^ O-7 HjC CN H3C H3C HO VS XSOjH 1 0 SC^ly^lH H3C02sX?SVN=N^ ^N^N=NH^K HaC H3C HO VS , unloading 3h 11 /S〇3H -./0^ f°3H p^tisC CCWHi Λ一一-free h3c h3c ho , so3h 12 SOjH .SO3H S—O ^HaC^jSN M NaNH^I HgC H3C HO, so3h 39 201006833 [Table 4] ¥¥¥] Knot No.

40 201006833

[table 5]

The diazotization of the compound represented by the above formula (10) is carried out by a method known per se 41 201006833. For example, 'in sulfuric acid, & acid, or phosphoric acid, for example, -5 to grasp, preferably 5 to 1 (the temperature of rc is carried out using nitrous acid to sulphuric acid. The compound represented by A (10) The coupling of the azo compound to the compound represented by the formula is also carried out under its own known conditions, for example, in water or an aqueous organic medium (a mixture of water and a water-soluble organic solvent, etc.), for example, -5 to 3 (TC, preferably 1 〇 to 3 〇〇 c temperature is implemented.

The compound represented by the formula U0) and the compound represented by the formula (11) are used in an amount approximately stoichiometric. The diazotization of the compound represented by the formula (12) is also carried out by a method known per se. In the presence of a mineral acid such as hydrochloric acid or sulfuric acid, it is, for example, _5 to 4 Torr, preferably 5 to 3 Torr in water or an aqueous organic medium. The degree of hydrazine is carried out using nitrite, for example, an alkali metal nitrite such as sodium nitrite. The coupling of the diazo compound of the compound represented by 4 (12) with the compound represented by the formula (13) is also carried out under the conditions known per se. For example, it is advantageously carried out in water or an aqueous organic medium at a temperature of, for example, ～50 ° C, preferably 1 Torr to 30 ° C, and at a weak acid to alkaline value. It is preferably carried out at a pH which is weakly acidic to weakly alkaline, for example, a pH of 6 to 〇. The diazotization reaction solution is acidic, and since the coupling reaction proceeds to further acidify the reaction system, it is preferred to adjust the above pH by adding a base. As the base, for example, a metal hydroxide such as a hydroxide or a sodium hydroxide; a metal carbonate such as carbonic acid clock, sodium carbonate or carbonic acid; an acetate such as sodium acetate; ammonia or an organic amine can be used. The compounds represented by the formulae (12) and (13) are used in an amount approximately stoichiometric. The diazotization of the compound of the formula (14) is also carried out by the method known per se 42 201006833. In the presence of a mineral acid such as salt, chlorpyrifos, hydrochloric acid or the like, it is preferably 10 to 3 in water or an aqueous organic medium (mixture of water and a water-soluble organic solvent, etc.). . . The temperature is carried out using nitrite, for example, using a nitrite metal salt such as sodium sulfoxide. The coupling of the diazo compound of the compound of the formula (14) and the compound represented by the formula (15) is also carried out under the article ''know''. For example, it is more advantageous to use a water or an aqueous organic medium at a temperature of -5 to 50 C, preferably 10 to 3 (rc, and a weakly acidic to an inspective P value. Preferably, it is weak. The pH value of the acidic to weakly alkaline, for example, the pH value of 6 to 1 and the pH value of *t丄, the adjustment of the pH value is carried out by adding the test. As the test, the same as above can be used. (1) The compound shown is a compound having a stoichiometric weight of 0. After the coupling reaction of the trisazo compound of the present invention, the addition of the desired inorganic salt or organic cation to the reaction solution is carried out or borrowed. Adding a mineral acid such as hydrochloric acid to a hot acid in the form of a free acid, and then using an acidic water or an aqueous organic medium, if necessary, after the salt, in the aqueous medium, Washing and removing the incompetence, ... using the desired inorganic or organic base to make the sum of the salt to make the corresponding salt, the liquid, the so-called acidic water, here will be such as sulfuric acid And an inorganic system such as hydrochloric acid, which is acidic. In addition, the so-called aqueous organic medium, An organic substance which can be mixed with water, and a plate which can be mixed with water, and the type of salt, such as a water-soluble organic solvent, which will be described later, may be exemplified by a negative medium, a machine, or a Examples of the alkali metal salt such as vaporized sodium or vaporized potassium and the salt of the ammonium salt such as ammonium sulfate or ammonium desert as an example of the salt of the organic cation of the above formula (9) include the organic amine (tetra) salt represented by the above formula (9). Examples of the inorganic test include, for example, hydroxides such as nitrogen oxide clocks, sodium oxychloride, and potassium oxyhydroxide, and hydroxides of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate; As an example of the organic test, an organic amine such as a quaternary class represented by the above formula (9), such as diethanolamine or triethanolamine, is exemplified, but is not limited thereto.

The ink composition of the present invention will be described. The aqueous ink composition containing the trisazo compound represented by the above formula (1) of the present invention can dye a material formed of cellulose. In addition, other materials having a carbon amide bond can be dyed, and can be widely used for dyeing leather, fabric, and paper. On the other hand, a representative use method of the compound of the present invention is exemplified by an ink composition formed in a liquid medium, and is particularly suitable as an ink composition for ink jet printing applications. The reaction liquid containing the trisazo compound of the present invention represented by the above formula (1) is, for example, an example described later! The reaction solution before salting out with sodium carbonate in ((4) 5) can be directly used for producing an ink composition. In addition, it may be first dried, for example, spray-dried, and inorganic salts such as vaporized milk, potassium carbonate, calcium carbonate, and sodium sulfate may be added to the field to perform salting out by adding inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. The acid precipitation is carried out; or the acid precipitation is carried out by combining the salting out and the acid precipitation, thereby separating the trisazo compound of the present invention and using it to prepare an ink composition. The ink composition of the present invention contains the formula (1 201006833) of the present invention, which is usually 〇·丨~2 〇, and has a shell weight %, preferably 1 to 10% by mass, more preferably 2 to 8 mass%. The third azo compound is shown and the remainder is a composition of the main medium of the water. The ink composition of the present invention may further contain, for example, hydrazine to 30% by mass of a water-soluble organic solvent, such as Bu 1 ( % by mass of the ink preparation agent. Further, other coloring matter may be contained in order to perform coloring or the like as needed. In this case, the total color of the pigment contained in the total mass of the Lishui composition is included in the coloring matter. The quality is within the above range.

The pH * ' of the ink composition is preferably from 5 to n, more preferably from 7 to 1 Torr, from the viewpoint of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 7 Å/m, more preferably 25 to 60 mN/m, and further, the viscosity of the ink composition is preferably 3 〇 mPa·s or less. More preferably 20mpa.s or less. The pH of the ink composition of the present invention and the surface tension can be appropriately adjusted by using a modifier and an surfactant as described below. The ink composition of the present invention is obtained by dissolving the above-mentioned arsenazo yttrium represented by the formula (丨) in water or a water-soluble organic solvent (an organic solvent which can be mixed with water), and adding an ink as needed. Agent. Other coloring matters and the like can be appropriately added to the diazo compound of the present invention in accordance with the purpose of preparing a neutral black ink composition. In the case where the ink composition is used as an ink for an inkjet printer, it is preferable to use a metal cation vapor or a sulfuric acid salt or the like as a tri-azo compound of the present invention. The standard of the content of the inorganic impurities is approximately equal to or less than the mass% of the total mass of the pigment. When the inorganic azo compound of the present invention is produced, for example, by a usual method using a reverse osmosis membrane, or by drying a dry product or a wet cake of the azo compound of the present invention in a 45 201006833 δ > granules It is only necessary to carry out desalination treatment by drying or the like of alcohol and water such as alcohol. Specific examples of the water-soluble organic solvent which can be used in the preparation of the ink composition of the above-mentioned ink composition include, for example, methanol, ethanol, propanol, isopropanol, decyl isobutanol, second butanol, and third butanol. Wait. ~ to anidiol; dimethylformamide, hydrazine, hydrazine-dimethyl hydrazine round lacking carboxy guanamine such as mercaptoacetamide; 2-pyrrolidone, -methyl 2 - ° ratio , Ν-methyl?...-ketone and other indoleamine; 3_Dimethylimidazolidin-2-one, 13- _A| ^ , monomethyl hexahydropyrimidine-2-one and other cyclic urea '--, methyl ethyl ketone, 2-methyl-2 · hydroxypentane _4 keto alcohol; four gas crunch, two-degree hospital and other ring shout; ethylene glycol, U propanediol, t-butanol, hydrazine-butanediol, M-hexanediol, two Ethylene, diethylene glycol, tetraethylene glycol, disulfide-glycan with polyethylene glycol, polypropylene glycol, decyl alcohol, etc., with 2~C6 alkylene units, mono- or poly-glycol or sulfur Glycol; glycerol, argon alcohol (alcohol W 1 calcined _1, 2, hexatriol and other polyethers, alcohol soap ether, diethylene glycol monomethylidene monoethyl ether, diethylene di-serine J ether (C-diether of a polyhydric alcohol such as butyl carbitol, mono-ol monomethyl ether or triethylene glycol monoethyl ether), a tetraalkyl group such as butyrolactone or a dimercaptosulfoxide may be used in combination of two or more. "Organic solvents can be used alone, as a preparation of the above ink composition, 々, WT WT 适 且 使用 使用 使用 使用 WT WT : : : : : : : 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防Chelating agent, water-soluble UV absorber, Water anti-solvent #丨, & / excitable polymer compound, acoustic de-sword, antioxidant, surfactant, etc.. Explanation] 茨寺试剂进行46 201006833 As a specific example of anti-mold agent, may be cited: dehydroacetate (- dehydroacetate), sodium benzoate, D-bite sulphur-small oxides, bis-ethyl formate, 12-benzoxanthene 4, oxazoline-3-one and its salts, etc. For the ink composition, 0 〇 2 〜 2 〇〇 mass % is used. As a preservative, you can cite, for example, an organic sulfur system, an organic nitrogen sulfur system, an organic halogen system, or a halogenated olefin.碲 碲 飒 、, iodopropynyl, Ν-Southern Sulphur, nitrile, pyridinium, 疋糸8-oxyquinoline, benzothiazole, 嗟 嗟 0 sit , dithiol system, 糸L drunk, pyridine pyridine, nitropropane, organotin, s, quaternary salt, triazine (8) (four), azine (""a- Aniline, radiant, dithiocarbamic acid, geranium, benzyl bromide, no, and salt As a specific example of the organic halogen-based compound, for example, a rebel can be used to carry out pentachlorobenine; and as a specific example of the acridine-based compound, for example, 2-pyridinethiol can be cited. 1. Oxide nano; as a specific example of the initial isothiazoline-based compound, for example, hydrazine, 2_benzisothiazolin-3-one, 2-n-octyl'-yl-4-isothiazoline_3 • Ketone, 5_gas_2_methyl-4-isothiazoline-3-ketone, 5-gas-2, rolling 2 methyl-4·isothiazolin-3-one magnesium oxide, 5-gas-2 -Methyl-4-iso-π-salt-sucking 1 fine, sitting on the _3-_ gasification calcium, 2-methyl-4-isothiasalin-3-one gasification about. Specific examples of the antiseptic and antifungal agent to be used include anhydrous sodium acetate, sodium sorbate, and sodium benzoate. As the pH adjuster, any substance can be used if it is possible to control the enthalpy of the ink to a range of, for example, 5 to u without adversely affecting the prepared ink. As a specific example of it, examples of the Cangjie Dan include, for example, diethanolamine, = ethanolamine, N-methyldiethanolamine, etc. Hydroxide; ammonia-vaporized ammonium (cyanide); lithium carbonate, 47 201006833 sodium carbonate, sodium bicarbonate, potassium carbonate and other acetic acid unloaded, such as carbonates; sodium sulphate, acid test metal salt Inorganic tests such as disodium acid disc. Specific examples of the reagent and the reagent include, for example, ethylenediaminetetraacetic acid monoacetate, sodium thioethylaminoacetate, diethylamine sodium pentaacetate, sodium uracil diacetate, and the like. —: Specific examples of the anti-recording agent exemplified are acidic sulfite, sodium sulphate, thioglycolic acid, diisopropyl nitrite tetranitrate, and dicyclohexylammonium nitrite. ^ Specific examples of the water-soluble ultraviolet absorber include, for example, a sulfonated benzophenone compound, a benzoxanthene compound, a salicylic acid, a sigma compound, a cinnamic acid compound, or Triazine compound. Specific examples of the water-soluble polymer compound include polyethylene glycol, cellulose derivatives, polyamines, and polyimines. Specific examples of the dye dissolving agent include ε_caprolactam, ethylene carbonate, urea, and the like. As a specific example of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Specific examples of the above-mentioned organic anti-fading agent include p-benzoquinone, alkoxyphene, di-oxybenzophenone, categor, aniline, amine, burn-in, and color-filled ( Eh_an), alkoxyaniline, heterocyclic, and the like. Specific examples of the surfactant include, for example, a known surfactant such as an anionic, cationic or nonionic surfactant. Specific examples of the anionic surfactant include an alkyl sulfonate, an alkyl carboxylate, an olefin sulfonate, a polyoxyethylene alkyl ether acetate, and 48 201006833 N-decylamino acid and salts thereof. N-mercaptopurine taurate, alkyl sulfate polyoxyalkyl sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl sulfate Salt, burnt-type sulphate, burnt-type acid vinegar, alkyl aryl acid salt, diethyl succinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinium Acid salt, etc. Specific examples of the cationic surfactant include a 2-vinylidene pyridine derivative and a poly-4-vinylpyridine derivative.

Specific examples of the amphoteric surfactant include: lauryl dimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-indole-ethylidene imidazoline rust betaine, and coconut oil fatty acid guanamine C. A dimethylaminoacetic acid betaine, a polyoctyl polyaminoethylglycine, or an imidazoline derivative.丨F sentence and carved in the world...Muscle q. Μ Μ中•不乳乙壬壬 Benzene shout, polyoxyethylene octyl benzene shout, polyoxyethylene dilute phenoyl benzene shout, polyoxyethylene ether ether, An ether system such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ether; oxirane oleate, polyoxyethylene bistearate, sorbitan laurate, sorbitol succinoic acid, Sorbitol liver monooleic acid vinegar, sorbitol wild sorghum oleic acid vinegar, polyoxyethylene oleic acid monooleic acid vinegar, polyoxyethylene stearic acid vinegar and other vinegar 22," '9-tetramethyl-5 癸 block ''Glycol and dimethyl octyl acetylene are used as acetylene diol (alcohol) such as ", -hexyne-3" alcohol, etc. As another specific example, ς f For example: Japanese Chemical Co., Ltd. Manufacturer of manufacturing. The name of the mouth is +11,4,1,5,82,465, and so on. These ink preparation agents can be used singly or in combination. The ink composition obtained by the above-mentioned respective components in an arbitrary order can be filtered by a 49 201006833 membrane filter or the like as needed to remove impurities. Further, in order to adjust the black color tone as the ink composition, in addition to the azo compound represented by the formula (1) of the present invention, other coloring agents having various color tones may be mixed. In this case, black or yellow with other shades can be used (for example, C I. Direct Yellow 34, 〇.1. Direct Yellow 58, 0:.1. Direct Yellow 86, (: 1 Direct Yellow 132, CI Direct Yellow 161, etc., orange (for example, C I. direct orange 17, c i. direct orange 26, CL direct orange 29, CL direct orange 39, CI. direct orange 49, etc.),

Brown, scarlet (such as CL direct red 89, etc.), red (for example, C丄 direct red 62, C丄 direct red 75, CI direct red π, direct red 8〇, CI direct red 84, (M• direct red 225, c丄 direct red 2%, etc.), magenta (such as CL direct red 227, etc.), purple, blue, navy, cyan, green, other colors of pigments are mixed and used. The ink composition of the present invention can be particularly long It is used in various fields, and is suitable for use in writing water-based inks, water-based printing inks, etc., especially for inkjet inks, and is suitable for use in the inkjet printing of the present invention described later. The inkjet printing method of the present invention will be described by inkjet. The invention is carried out ==(4) is characterized in that the ink composition of the present invention is used for the preparation of the ink recording method. In the above black inkjet printing method of the present invention, In the case of inkjet recording containing an ink composition, it is appropriately selected by recording on the recording material in the evening. The nozzle or the like is not particularly limited, and a known method can be used for the purpose of controlling the charge control method. ; Utilize: controllable spray using the electrostatic attraction force to make the piezoelectric nozzle 7L vibration pressure 50 201006833 On-demand mode (pressure pulse mode becomes the sound beam and irradiates the ink, using it to release the ink == mode The ink is heated to form a bubble, and the thermal inkjet of the force is used, that is, the bubble inkjet (registered trademark) method, etc. The above inkjet printing method also includes: Ink in the ink (pigment content) 16 ink

A method of multi-strand; a method of improving the image quality by using a plurality of inks having different concentrations in the ink in substantially the same color tone; (4) a method of colorless and transparent ink. The coloring system of the present invention is colored by the above-described compound of the present invention represented by the formula (1) or an ink composition containing the same, more preferably by an inkjet printing method using a machine, and the ink composition of the present invention is recorded. Record material for coloring. The material to be recorded which is colored is not particularly limited, and examples thereof include: sheets for information transmission such as paper and film; fibers or cloth (such as cellulose, nylon, wool, etc.), leather, and substrates for color filters, and the like. Preferably, the sheet for eccentric transfer of the information transmission material is preferably a surface-treated one, specifically, an ink absorbing layer provided on a substrate such as paper, synthetic paper or film. The ink absorbing layer may be, for example, a method of immersing or coating a cationic sulphide on the above-mentioned substrate; inorganic granules which absorb the pigment in the ink, such as porous sulphur dioxide, oxidized, and special ceramics, Ethylene glycol, polyethylene, sputum, _, etc., the hydrophilic polymer is applied together on the surface of the above substrate. 51 201006833 Fecal use a a Such ink absorbing layer is usually called inkjet paper, inkjet Special film, glossy paper, glossy film, etc. The sheet of the white inorganic material for the above-mentioned information transmission is mainly shown in Table 2: The surface is coated with a porous surface, and the surface is high in water resistance, so it is particularly suitable for the printing of photographic images. Images recorded on these may become discolored or faded due to ozone gas. Of course

On the other hand, the ink composition of the present invention is excellent in ozone gas resistance, so that the recording material is subjected to such a large effect as in the case of ink printing. As an example of a representative commercial product of a sheet having a porous white inorganic material coated on the surface as described above, there is a product name: Pr〇feSsi〇nal Phot〇Paper manufactured by CanGn. Super ph〇t〇pap", Gloss Gold, and Matt Ph〇t〇paper; ~ Know Ep with (stock) manufacturing. Name. Photo paper CdspU (high gloss), photo paper (gloss), Photo Matt paper Product name manufactured by Hewleu_packard Co., Ltd.: Advance Photo paper (gloss); trade name manufactured by FUm (share): enamel photo processing pro, etc. Evaluation of the inkjet printing method of the present invention for information transmission sheets When recording on the material to be recorded, for example, the container containing the ink composition is loaded on a specific position of the ink jet printer, and recording can be performed on the material to be recorded by a usual method. The method may also employ the black ink composition of the present invention with inks of various colors such as known magenta, cyan, yellow, and optionally green, blue (or purple), and red (or orange) colors. 52 201006833 The ink compositions of the respective colors are injected into the respective containers, and the containers are loaded in a specific position of the ink jet printer for inkjet printing in the same manner as the container containing the black ink composition of the present invention. The triazo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing the compound as a dye does not precipitate for a long period of time. Solid precipitation, physical property change, color tone change, etc., and storage stability is good. Further, the ink composition containing the trisazo compound of the present invention can be used for ink jet printing or writing instruments. Further, when printing on a sheet for information transfer, particularly inkjet paper, the printed image is printed. The printing density is high, and various durability of the printed image is excellent, that is, water resistance, gas resistance, moisture resistance, and particularly ozone gas resistance and light resistance. [Examples] The present invention will be more specifically described, but the present invention is not limited by the following examples. Ming, the "parts" and Γ% "as the quality benchmark. Further, in the following formulas, functional groups such as a sulfo group and a carboxyl group are represented by a free acid. Further, the pH value and the reaction temperature described below indicate the measured values in the reaction system. Further, the maximum absorption wavelength (λ max) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value of the compound of the referenced 2010 201006833 is described in the examples. Further, the synthesized invention has a solubility of 100 g/L or more. The three azo compounds are all expressed in water [Example 1] ❿ I芡1) After 20 parts of 2-aminobenzothiophene in 2〇~ parts of 30〇/〇 fuming sulfuric acid, slowly After addition to 180, the precipitates (4) and (4) were separated and borrowed/to 158 parts of the indicated compound in ice water. Thereby, 14.4 parts of the following formula are obtained [Chemical Formula 16]

(16)

(Step 2) Dissolve 124 parts of the compound represented by the above formula (16) in (10) parts of 97% sulfuric acid, add 75 parts of water under _, and suspend it, and add 4.3 parts of 60/"chamoic acid". Adding 2 parts of 40% nitrosyl sulphuric acid 'sodium sulphate' at a temperature of 5 to 1 〇〇c for about 1 hour to obtain a diazo reaction solution. On the other hand, 'in 130 parts of water 10.8 parts of the compound of the following formula (17), 8.0 parts of the aminosulfonic acid were added, followed by the addition of sodium hydroxide so that the pH of 54 201006833 was 5. 〇~5.5 ' thereby obtaining an aqueous solution. In the reaction temperature of °C, the above-mentioned diazo reaction f is added dropwise in about 2 parts of the solution. After the completion of the dropwise addition, the mixture is given at the same temperature for 1 hour, and 400 wounds are added. The wet cake of the compound of (U) is obtained by the filtration and separation of the precipitated solids, and the following formula is obtained by the following formula (the compound represented by the following formula (U), which is described in JP-A-2004-083492 The method of obtaining is obtained. Patent [Chemical Formula 17]

[Chemical Formula 18]

(18) π3. (Step 3) 1 7) The compound shown in Fig. 5 is obtained by adding 5.4 parts of the above formula to 35 parts of water, followed by adding sodium hydroxide to bring the pH to 5 〇 solution. On the other hand, the wet cake obtained in the above (Step 2) was added to the water of the U sputum under stirring, and then, sodium hydride was added so as to have a pH of 7. 〇 to 7.5, whereby an aqueous solution was obtained. 55 201006833 Add 4 6 a ^ 35% hydrochloric acid to the obtained aqueous solution, and then add 5.0 parts of 40% sodium nitrite aqueous solution at a reaction temperature of 15 to 20 C with about 5 minutes and a female knife fin. When the reaction is small, the diazo reaction solution is obtained in the wrong manner. The obtained diazo reaction solution was added dropwise from an aqueous solution containing a compound of the formula (丨7) obtained in the same manner as the previous method at a reaction temperature of 20 to 30 ° C for about 20 minutes. Danshui added sodium carbonate to the reaction system to maintain the pH at 5. 〇~5 4 Λ ^ . After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added thereto, and salting out was carried out, and the precipitated solid was separated by filtration, whereby a wet cake containing the compound represented by the following (丨9) was obtained. . [Chemical Formula 19]

(19) (Step 4) The wet cake containing the compound of the formula (19) obtained by the above-mentioned (Step 3) in the glyphs is dissolved in 15 parts of the skin φ pseudo-water Add 4.1 parts of 35% hydrochloric acid dropwise, and then add 20 parts of 40% sodium nitrite solution to the anti-corridor at 20~25°C, Tianfu v, and Han should be added in about 5 minutes. In particular, Han is willing to take 1 hour to obtain a diazo reaction solution. In another aspect, 2 to 4 parts of the compound of the following formula (2〇), which is obtained by the method of Patent Document 8, is added to 55 parts of water, and then the wind oxide is added so that the enthalpy is 7.5 to 8 Hey, and get an aqueous solution. The diazo reaction solution obtained as described above was added dropwise to the aqueous solution at about 30 minutes from the reaction temperature of 56 201006833 30 C. In the meantime, sodium carbonate was added to the reaction system to maintain the pH at 7.0 to 8,0. After the completion of the dropwise addition, the mixture was dropped for 2 hours at the same temperature, and gasification was carried out to carry out salting out, and the precipitated solid 11 was separated by filtration, whereby a wet cake was obtained. The wet cake obtained was dissolved in 160 parts of water, and after 350 parts of the network was added, the precipitated solid was separated by filtration, whereby a wet cake was obtained. The obtained wet cake is redissolved in 110 parts of water Φ. After adding 280 parts of acetone, the precipitated solid is passed through the knife, and the compound shown in the following formula ((1) is obtained. This hair) comes as a salt. & matter (combination of N〇.3 in Table 2 and max: 575 nm. [Chemical Formula 20] ❿ Η

(20) [Chemical Formula 21]

[Example 2] 57 (21) 201006833 A mixture of 17.1 parts of anal gas · 3 · nitrotoluene, 22.0 parts of 3-sulfopropane sodium sulphate, and 60 parts of dimethyl sulfoxide was stirred under Heating to 60 C ' At this time, 11.2 parts of sodium carbonate was added. After the addition, it was heated to 12 〇 to 130 ° C and stirred at the same temperature for 6 hours. After cooling the reaction mixture to room temperature, it was added to 33 parts of 2-propanol with stirring. The precipitated solid was separated by ’ and washed with 100 parts of 2-propanol. After the obtained solid was added to 300 parts of water, the pH was 7.0 to 7.5 with 35% hydrochloric acid, salting out was carried out by adding sodium carbonate, and the precipitate was separated by filtration to obtain the following formula. (22) A wet cake of the compound shown. [Chemical Formula 22]

(22) (Step 2) 16.6 parts of iron powder, 12 parts of water, and 31 parts of 35% hydrochloric acid were heated to 9 CTC under stirring. (4) After 40 minutes, in the solution, the above (Step 1) is added dropwise in about 15 minutes; the wet cake containing the compound represented by the above formula (22) is suspended in 6 parts of w < a solution that is paid in water. After the dropwise addition, the reaction solution was stirred at 85 to 9 (TC for 2 hours, and then cooled to room temperature. After the insoluble matter was filtered off, 35% hydrochloric acid was added, and the solid precipitated by the acid precipitation was separated by filtration and dried. After that, 16.7 parts of a compound represented by the formula (23) were obtained. [Chemical Formula 23] 58 (23) 201006833

(Step 3) In place of (10) parts of the solution (Step 2) of Example 1 except that 11.5 parts of the aqueous solution of the compound of the above formula (23) obtained in (Step 2) of Example 2 was used. The compound represented by the following formula (24) of the present invention obtained in the same manner as in Example 1 except for the compound represented by the above formula (17) (version 2 in Table 2) The compound) is used as a sodium salt. λ max : 585 nm 〇 [Chemical Formula 24]

[Example 3] [(A) Preparation of Ink] The black ink composition of the present invention was obtained by mixing the respective %~preparation components described in the following Table 6 to 'utilize Λ^ ϋ·45 # The membrane filter of m filters out impurities, thereby obtaining ink. The preparation of this ink was taken as Example 3. In addition, the water system uses ion-exchanged water. In the preparation of the ink, the pH of the ink 2010 201006833 is determined by using sodium hydroxide .9 and the amount of t is made to be 1 part by adding ion-exchanged water. This hair is especially suitable for "The water-based black ink does not cause separation during storage" and does not cause physical property changes even after long-term storage. Beyond Kings [Table 6] Glycerin---- 3,5 5.0 parts of lysine 5.0 parts of T-based-2-° brothel ketone 4.0 parts _ isopropyl alcohol ^ '--- 3.0 parts of butyl carbitol 2.0 parts of surfactant (trade name: Surfynoll04's manufactured by Nissin Chemical Co., Ltd.) 0.1 part water + hydrogen hydrogenated sodium 77.4 parts total 100.0 parts [Comparative Example 1] The following formula comparison words

Water was prepared in the same manner as in Example 3, except that the coloring matter of (25) disclosed in Examples 2 to 6 of Patent Document 8 was used instead of the compound of Example 2 as the black coloring matter. This was taken as Comparative Example 1. [Chemical Formula 25]

[(B) Inkjet Printing] 60 201006833 Using the inks obtained in the above, using an inkjet printer manufactured by Canon, under the trade name PIXUS iP4100, in Glossy Paper 1 (manufactured by Can〇n, trade name Canon photo paper glossy Gold GL-101A450), glossy paper 2 (manufactured by Seiko Epson, trade name Crispia (high gloss) KA420SCK), glossy paper 3 (made by Seiko EPson, trade name photo paper (gloss)) KA420PSK ) : The ink recording on the three kinds of information recording sheets (inkjet paper). • At the time of printing, an image pattern is produced by obtaining the reflection density in several stages of gray scale to obtain a black print. [(C) Evaluation of Recorded Image] For each of the printed images obtained by using the inks prepared in Example 3 and Comparative Example 1, the change in the density of the image before and after the test for the light resistance and the ozone gas resistance evaluation of. Further, each of the printed images was dried at room temperature for 24 hours or more after printing. The density change of the printed image is GRETAG-MACBETH. The color measuring machine is manufactured by SpectroEye, and the black reflection density Dk of the printed image before the test is in the range of 丨.2~1 ·4. The gray scale portion was measured by color measurement. When the black reflection density Dk value is measured, mN is used as a concentration reference. Further, the test was carried out separately for the glossy paper, and the test results are shown in Table 7. The specific test method is as follows. 1) Ozone-resistant gas resistance test 61 201006833 Using the Ozone Weatherometer manufactured by Suga Test Machine Co., Ltd., each printed image has a concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24. . Place under the conditions of (: 8 hours). After the test, use the above color measuring machine to measure the color, and (the black reflection density Dk value after the test / the black reflection density Dk value before the test) χ 1 〇〇 (%) The calculation formula was used to calculate the residual ratio of the dye of each printed image. The test results were evaluated according to the following criteria: ◎ : Residual rate was 90% or more 〇: Residual rate was 80% or more, less than 900/〇 Δ: Residual rate 70% or more and less than 80 〇/〇X: Residual rate is less than 70% 2) Light resistance test using the product name "LOW-temperature 氙 weathering tester XL75" manufactured by Suga Testing Machine Co., Ltd. at illuminance of 1 million lux, humidity For the condition of 6〇%rh and temperature C, after the above-mentioned respective printed images were irradiated for 168 hours, the color measuring machine was used to measure the color 'and the black reflection density Dk after the test/before the test The calculation formula of the black reflection density Dk value xl 〇〇 (%) is used to calculate the residual ratio of the pigment of each printed image. The test results were evaluated based on the following criteria. ◎: Residual rate is 80% or more 0: Residual rate is 70% or more and less than 8〇% Δ: Residual rate is 50% or more and less than 7〇% X: Residual rate is less than 50% [Table 7] 62 201006833 Ozone-resistant gas Optically-optical Example 3 (Formula (24)) Glossy Paper 1 ◎ ◎ Glossy Paper 2 ◎ ◎ Glossy Paper 3 ◎ ◎ Comparative Example 1 (Formula (25)) Glossy Paper 1 〇 ◎ Glossy Paper 2 〇 ◎ Glossy Paper 3 〇◎

As is clear from the results of Table 7, the printed image of Example 3 and the image of Comparative Example 1 were compared with the results of the ozone gas resistance test of each glossy paper. Good results. In other words, in the case of using any of the glossy papers, the pigment residual ratio is 80% or more and less than 90%. In contrast, in the case of using any of the glossy papers in Example 3 of the present invention, the pigment remains. The rates are shown as (4) or more. From this, it was found that the ozone-resistant gas resistance of each of the examples was extremely excellent with respect to the comparative examples. In the light resistance test, although the difference from the comparative example was not shown, in Example 3, in any of the glossy papers, the residual ratio of the dye showed a very high light resistance of (10)%, and it was found that the light resistance was also improved. Extremely excellent. According to the above results, it is understood that 'the firmness of the printed image obtained by using the ink immersion containing the trisazo compound of the present invention is superior to the image of the conventional trisazo nitride used in the comparative example. #, In particular, it is an extremely excellent pigment in terms of ozone gas resistance and richness required for inkjet P-brush images. [Industrial Applicability] The ink composition containing the trisazo compound of the present invention is suitably used as a black ink for inkjet printing or writing instruments. 63 201006833 [Simple description of the diagram] None [Main component symbol description]

Claims (1)

201006833 VII. Patent Application Range: 1- A trisazo compound or a tautomer thereof, or a salt thereof, wherein the trisazo compound is represented by the following formula (1), [Chemical Formula 1] (In the formula (1), R1 is a carboxyl group, a C1 to C4 alkyl group which is unsubstituted or substituted by a carboxyl group, or a phenyl group which is unsubstituted or reductively substituted, and R2 is a cyano group, an amine formamyl group, or a carboxyl group. , R and R are each independently a hydrogen atom, a chlorine atom, a base group, an unsubstituted C1 to C4 alkyl group, or an unsubstituted ci~C4 alkoxy group, and a ring substituted by R5 to R' is shown by a dotted line. When the ring is not present, it is a stupid ring, in the presence of a ring shown by a broken line, it is a naphthalene ring, and R5 to R7 each independently represent a hydrogen atom; a chlorine atom; a transradical; a contiguous group; a few groups; an amine sulfhydryl group; Stuffed base; unsubstituted C1~C 4 base; unsubstituted 'or substituted with hydroxy, unsubstituted C 1 -C4 alkoxy, via a C1 to C4 alkoxy group, a sulfo group, or a thiol group a C1 to C4 alkoxy group; a mono- or di-c丨~C4 alkylamino group which is unsubstituted or substituted by a hydroxy group, a sulfo group or a carboxyl group; an unsubstituted or C1 to C4 alkane substituted by a hydroxy group or a carboxyl group Alkylcarbonylamino; unsubstituted, or N'-C 1 -C4 alkylureido substituted by hydroxy, sulfo, or thiol; unsubstituted, or benzene ring by gas 65 201 006833 An alkyl group, a nitro group, a sulfo group, or a carboxy group substituted or a phenyl ring substituted with a gas atom, an unsubstituted or a carboxyl group; a benzylamino group; an unsubstituted group or a C1 to C4 alkane a phenyl group, a nitro group, a sulfo group, or an unsubstituted, or a phenyl ring via a gas atom, an unsubstituted ci~ a sulfoalkylamino group substituted with an alkyl group, a nitro group, a sulfo group, or a carboxyl group, R to The ring substituted by R1Q is a benzene ring when the ring shown by the dotted line is not present, and is a naphthalene ring in the presence of a ring indicated by a broken line, and R8 to R1G independently represent a hydrogen atom; a gas atom; a hydroxyl group; a sulfo group; Amine sulfonyl; amine carbhydryl; unsubstituted C1 to C4 alkyl; unsubstituted, or hydroxy, unsubstituted C1 to C4 alkoxy, hydroxy C1 to C4 alkoxy, sulfo group Or a carboxyl group substituted to alkoxy; unsubstituted, or substituted by a hydroxy, sulfo, or carboxyl group; C1 to C4 alkylthio; unsubstituted, or substituted by hydroxy, sulfo, or carboxy Or a C1 to C4 alkylamino group; unsubstituted or substituted by a hydroxyl group or a carboxyl group; C1 to C4 alkylcarbonylamino group; Substituted, or substituted with a hydroxyl group, a sulfo group, or a carboxyl group, N|-C1 to C4 alkylureido; unsubstituted, or a benzene ring via a chlorine atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group Or a phenylamino group substituted with a sulfhydryl group; an unsubstituted or benzoylamino group substituted with a gas atom, an unsubstituted C1 to C4 alkyl 'nitro group, a sulfo group, or a carboxyl group; Unsubstituted, or a phenyl sulfonylamino group substituted with a benzene ring via a gas atom, an unsubstituted C1 to C4 alkyl group, a nitro group, a sulfo group, or a carboxyl group, the group A being unsubstituted or having a substituent a benzothiazolyl group; a thiadiazolyl group; or a 嗟η seating group, which may have a substituent selected from the group consisting of 66 201006833 from a chlorine atom; a thiol group; a nitro group; a hydroxyl group; Sulfhydryl; unsubstituted C1 to C4 alkyl; unsubstituted, or C1 to C4 alkoxy substituted by hydroxy, C1 to C4 alkoxy, terminic, or carboxy; unsubstituted, or a C1~C4 alkylsulfonyl group substituted with a sulfo group or a carboxy group; and unsubstituted or a benzene ring passing through a chlorine atom a group consisting of a group consisting of a c 丨 C4 alkyl group, a nitro group, a sulfo group, or a carboxy group substituted phenyl sulfonyl group, and a substituent, wherein the thiadiazolyl group or the thiazolyl group has a substituent When it may be selected from the group consisting of: a gas atom; a sulfo group; a nitro group; a hydroxyl group; an amine sulfonyl group; a fluorenyl group; and, unsubstituted, or via a hydroxyl group, a C1 to C4 alkoxy group, a hydroxy hydrazine to a C4 silk group. a substituent in the group consisting of a thiol group or a thio group substituted by a silk). 2. The diazo compound or its tautomer, or the salt thereof, as described in the first paragraph of the patent application, wherein the compound of the above formula (1) The trisazo compound represented by the following formula (2), [Chemical Formula 2] A -1^1 (In the formula (2), 'the base A, ri to the mouth|〇〇K to R, and the ring substituted by the Han 8 to Ru, including the ring shown by the broken line is the meat emulsion, "inside, both have the formula (1) The same meaning as described in the above-mentioned patent. The compound of the above formula or the tautomer thereof is as follows: Formula (3) represents diazotization [Chemical Formula 3] R] to (in the formula (3), the meaning of the base A). R has the same formula as in formula (1). 4. The trisazo compound deuterium ortho-isomer, iUtfU I or its enthalpy as described in the scope of claim 1 of the & i field* (1) represented by trisazotization The compound is represented by the following formula (4), [Chemical Formula 4] Base A, Ri to R, and R8 to R1. Has the same meaning as formula (1), 68 201006833 R5 and R7 each independently represent a hydrogen atom; unsubstituted C1~C4 courtyard group; or 'unsubstituted' or C 1~C4 alkoxy substituted by sulfo or hydroxy group Base; R6 represents a hydrogen atom). 5. The trisazo compound or the tautomer thereof as described in claim 1, wherein the isomer or the salt thereof, wherein the trisazo compound represented by the above formula (1) is Equation (5) indicates that φ [Chemical Formula 5] (In the formula (5), the group A, R1 to R4 have R5 and R7, and the C1 to C4 anisles C1 to C4 alkoxy groups which are independently unsubstituted with the formulae R to R1G, respectively; or a group; and R9 represents a hydrogen atom) . And R has the same meaning as in the formula (1), and has the same meaning as the formula (4), and 1 each independently represents a hydrogen atom; a sulfo group C 1 to r C1 to C4 alkyl; unsubstituted, or a C1^C1~C4 alkoxy group substituted by a hydrazine group or a group; or a C1~C4 alkyl sulphate substituted by a sulfo group, as in the scope of the patent application, an isomer, an initial, or a salt thereof, [Chemical Formula 6 Θ 1 of the basic A 69 (6) 201006833 (In the formula (6), R to R13 each independently represent a hydrogen atom; a gas atom; a sulfo group; a nitro group; an amine group; a C1 to C4 alkyl group; an unsubstituted group, or a (4) group, a C group not substituted by 4 ～C4 alkoxy, 4, or a substituted C1~C4 • alkoxy; or, unsubstituted, or substituted by a phenyl, thiol or a sulfhydryl group; . The tris-oxygen compound or a tautomer thereof according to the first aspect of the invention, or a salt thereof, wherein the methyl group, R is a cyano group or an amine carbenyl group, R is a hydrogen atom, and R4 is Sulfo. 8 The trisazo compound or its tautomers described in the first paragraph of the patent scope, or the salts thereof, ^, R6 Λ . 7 ', R is sulfopropoxy or sulfobutoxy Is a hydrogen atom, and R is a hydrogen atom, a methyl group or an ethyl group. 9. If the patent application is in the first item, +, * y ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Free. Hydrogen atom; chlorine atom; sulfhydryl group; Shixiao history by · ·, replaced by sulfo or carboxyl group c ' u laugh 1 ~ C4 alkylthio group composed of 70 068 70 201006833 10. Apply for patent Scope 6 Item 2 azo compounds or their tautomers, or such salts, of which! Preparation 1 n4 Dan TR is a methyl group, R2 is a cyano group, R3 is a hydrogen atom, R is a repeating group, r5& 8 R is a sulfopropoxy group. R6 is a hydrogen atom, R? is a methyl group, and R is a sulfonate. The propylthio group 'r9 is a hydrogen atom, r1〇 is a methyl group, and two of Rn to R13 are a sulfo group and one is a hydrogen atom. An ink composition containing the meta isomer according to any one of items 1 to 10, or a salt thereof, as one of the pigments, or a diazo compound as described above. An inkjet printing method in which an ink composition as described in the above-mentioned Patent Application No. 11 is used as an ink, and ink droplets of the ink are ejected according to a recording signal and attached to a material to be recorded. With this, print it. The inkjet printing method according to Item 2 of the above-mentioned application, wherein the recording material in the inkjet printing method is a sheet for information transmission. The inkjet printing method according to claim 13, wherein the sheet for information transmission has a sheet containing an ink absorbing layer of a porous white inorganic material. 71. The invention relates to a tris-azo compound or a tautomer thereof according to any one of the above-mentioned claims, the first aspect of the invention, or the tautomer thereof, or the like Salt is colored. 72 201006833 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this 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: 201006833 ^ Chromium π Year The patent number "year, beta month sweat 15" - an ink jet printer 'filled with a container containing the ink composition as described in the above 11). 16) - a color body, by The trisazo compound or a tautomer thereof according to any one of the above items 1) to 1), or a salt thereof, is colored. [Effects] The trisazo compound of the present invention or a tautomer thereof Or such a salt, which has a high solubility in a medium containing water as a main component, and is also stable in the case of storing a high-concentration aqueous solution or ink of the compound for a long period of time, and the printed image is The concentration is very high, and the synthesis thereof is easy and inexpensive, and the properties are good. Further, the ink composition containing the three substances of the present invention or the salts thereof is suitable for the diazo compound of the present invention or a tautomer thereof, or the like Since the salt is excellent in water solubility, the filter property by the membrane filter is good in the process of producing the ink composition, and the ink composition containing the compound or the ink prepared from the ink composition is preserved. Stability or spray It is also excellent in stability. That is, the ink composition of the present invention containing the trisazo compound or the tautomer or the salt does not cause solid precipitation, physical property change, color change, etc. after long-term storage. Stable trisazo compound or its tautomerism , special 13 201006833 \ , the first stipulation project w years, the 0 month amendment 10. If you please patent _ the sixth three reduction compounds or their mutual changes, or the salt, where R1 is methyl , R, cyano, R3 is a hydrogen atom 'R4 is a terminus, r5 is a repeating dioxy group, r6 is a nitrogen atom, r7 is a methyl group, R8 is a thiopropylthio group, r9 is a gas atom, r1〇 is The methyl group, two of R11 to R are a sulfo group and one is a hydrogen atom. ❿ U. An ink composition comprising at least one tris-I compound or a tautomer thereof according to any one of the above-mentioned claims 1 to 1G, or a salt thereof as a pigment . 12. An inkjet printing method in which an ink composition as described in the above item 5 of the above-mentioned patent application is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal and attached to a material to be recorded. With this, print it. The inkjet printing method according to claim 12, wherein the recording material in the inkjet printing method is a sheet for information transmission. 14. The inkjet printing method according to Item 13, wherein the information transfer sheet #' has a sheet containing an ink absorbing layer of a porous white inorganic material. An ink jet printer which is filled with a container comprising the ink composition as described in the above-mentioned patent application. 71