WO2004013232A1 - Trisazo compounds, water-base ink compositions, and colored articles - Google Patents

Abstract

Trisazo compounds represented by the general formulae (1-1) and (1-2) or salts thereof; and ink compositions containing the same: (1-1) (1-2) (wherein R1 is hydrogen, C1-4 alkyl, or C1-4 alkoxy; and A is a group represented by the general formula (2) or (3) which is bonded to the above skeletal structure at the 2- or 3-position: (2) (3) (wherein R2 to R11 are each an arbitrary substituent)). The ink compositions are useful for ink-jet recording and writing tools and can give recorded images which have high density and are excellent in ozone gas resistance, light fastness, water resistance, and color rendition. Further, the compositions are excellent in shelf stability as recording fluid.

Description

 Specification

 Trisazo compound, aqueous ink composition and colored body

 TECHNICAL FIELD The present invention relates to a novel water-soluble trisazo compound or a salt thereof, an aqueous ink composition containing the compound and a colored product thereof. Background art

Among the various color recording methods, a recording method using an ink jet printer, which is one of the representative methods, generates ink droplets and attaches them to various recording materials (paper, film, cloth, etc.). It is for recording. This method has been rapidly spreading in recent years because it has low noise and quietness because the recording head does not come into contact with the recording material. Growth is expected. Conventionally, water-based inks in which a water-soluble dye is dissolved in an aqueous medium have been used as ink for ink such as fountain pens and felt pens, and ink-jet recording inks. In general, a water-soluble organic solvent is added to prevent ink clogging. With these conventional inks, it is necessary to provide a recorded image with sufficient density, not to cause clogging of the pen tip and nozzle, to have good drying properties on the recording material, to have little bleeding, and to have stable storage. It is required that the image has excellent fastness and the like, and the formed image is required to have fastness such as water fastness, light fastness, moisture fastness and ozone gas fastness. Ozone gas resistance refers to resistance to the phenomenon that oxidizing ozone gas present in the air reacts with a dye on a recording paper or in a recording paper, causing discoloration of a printed image. This ozone gas is considered to be a causative substance for promoting the fading phenomenon of the ink jet recorded image. Since this discoloration and fading phenomenon is characteristic of ink jet images, improving ozone gas resistance is an important issue. In particular, the ink-receiving layer provided on the surface of photographic quality inkjet paper is made of a porous material to accelerate drying of the ink and reduce bleeding with high image quality. In many cases, discoloration due to ozone gas is remarkably observed on such recording paper.

 In the future, when used in exhibitions such as advertisements in order to expand the field of use of ink-based printing methods, they will be exposed to light (electric lights, fluorescent lights, sunlight, etc.) in many cases. In addition to water resistance, light resistance, and moisture resistance, there is a strong demand for an ink composition to be used and a colored body colored therewith, in particular, an improvement in ozone gas resistance.

 Different hue inks have been prepared from different dyes, of which black ink is an important ink used for both mono and full color images. To date, a great number of patent applications have been filed as dyes for these black inks (for example, JP-A-2-140270, JP-A-3-167270, JP-A-3-200852, JP-A-4-159065, JP-A-6-290). — 172668, JP-A-6-124812, JP-A-7-26160, JP-A-7-268256, JP-A-8-245894, International Publication W00-Z43451, WO00 / 43453, etc.) However, it has not yet been able to provide products that fully satisfy market requirements. Disclosure of the invention

 INDUSTRIAL APPLICABILITY The present invention has high solubility in a medium containing water as a main component, is stable even when a high-concentration aqueous dye solution and ink are stored for a long period of time, has a high density of a printed image, and has moisture resistance, light resistance, An object of the present invention is to provide an ink composition which gives a black recorded image having excellent ozone gas resistance.

 The present inventors have conducted intensive studies to solve the problems described above, and as a result, have reached the present invention. That is, the present invention

(1) a trisazo compound represented by the following general formula (1-1) or general formula (1-2) or a salt thereof,

(Wherein, R ¹ is hydrogen; (C ¹ -C 4) an alkyl group; (C ¹ -C 4) an alkoxy group; A represents the general formula (2) or the general formula (3); Second or third place.)

(In the formula (2), R ² to R ⁶ represent an arbitrary substituent.)

(In the formula (3), R ⁷ to R ¹¹ represent an arbitrary substituent.)

(2) R ² and R \ R ^{4 in the} general formula (2) or R ⁷ and RR ^{9 in the} general formula (3) are each independently a hydrogen atom; a hydroxyl group; an amino group; a carboxyl group; Or a (C 1 -C 4) alkyl group having at least one substituent selected from the group consisting of a hydroxyl group and a (C 1 -C 4) alkoxy group as a substituent; a hydroxyl group and a (C 1 -C 4) (C1-C4) alkoxy having at least one substituent selected from the group consisting of Coxy group; one or more selected from the group consisting of an unsubstituted or substituted (C1-C4) alkyl group, an unsubstituted or substituted (C1-C4) alkanol group, an unsubstituted or substituted phenyl group; A mono- or di-substituted amino group substituted by two types, provided that the substituent on the substituted alkyl group or the substituted alkanol group is at least one selected from the group consisting of a hydroxyl group, a (C 1 -C 4) alkoxy group and a hydroxyl group; Wherein the substituent on the substituted phenyl group is at least one selected from the group consisting of a sulfoxyl group, a sulfonate group and an amino group); a sulfonic acid group; a halogen atom or a peridode group; R ⁵ and R ^{6 of} formula (3) or R ^1Q and R ¹¹ of formula (3) are each independently a hydroxyl group; an amino group; (C 1 -C 4) alkoxy group; unsubstituted or substituted as a substituent (C1-C5) alkyl group, unsubstituted or substituted (C1-C4) alkanoyl group, unsubstituted or substituted phenyl group, mono- or disubstituted amino group substituted with one or two kinds selected from the group consisting of The substituent on the substituted alkyl group or the substituted alkanol group is at least one selected from the group consisting of a hydroxyl group, a sulfonic acid group, a (C1-C4) alkoxy group and a carbonyl group; The substituent is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, a hydroxyl group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group and a halogen) The trisazo compound or salt thereof according to the above (1), which is:

(3) In the general formula (2), R ² , R ³ , and R ⁴ each independently represent a hydrogen atom; a hydroxyl group; an amino group; an amino group; a carbonyl group; a hydroxyl group or a (C 1 -C 4) alkoxy group. (C1-C4) alkyl group which may be substituted; hydroxyl group or (C1-C4) alkoxy group which may be substituted by hydroxyl group or (C1-C4) alkoxy group; hydroxyl group or (C1-C4) ) Mono- or di- (C 1 -C 4) alkylamino groups which may be substituted by alkoxy groups; carboxylic acid (C 1 -C 5) alkylamino groups or bis- [functional lipoxy- (C 1 -C 5) alkyl] amino groups A (C1-C4) alkanoylamino group which may be substituted by a hydroxyl group or a (C1-C4) alkoxy group; substituted by a carbonyl group, a sulfonic acid group or an amino group. A phenylamino group; a sulfonic acid group; a halogen atom or a peridode group, wherein R ⁵ and R ⁶ are each independently a hydroxyl group; an amino group; a (C 1 -C 4) alkoxy group; ) (C1-C4) alkylamino groups optionally substituted by alkoxy groups;

(C1-C5) alkyl] amino group or bis- [carboxy- (C1-C5) alkyl] amino group; mono- [sulfo (C1-C5) alkyl] amino group or bis- [sulfo (C1-C5 C5) Alkyl] amino group; may be substituted with carbonyl group, sulfonate group, amino group, hydroxyl group, (C1-C4) alkyl group, (C1-C4) alkoxy group or halogen R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom; a hydroxyl group; an amino group; a carbonyl group; a hydroxyl group or a (C 1 -C 4) alkoxy group. (C1-C4) alkyl group which may be substituted; hydroxyl group or (C1-C4) alkoxy group which may be substituted by hydroxyl group or (C1-C4) alkoxy group; hydroxyl group or (C1-C4) ) Alkoxy group A (C 1 -C 4) alkylamino group optionally substituted by: a carboxylic acid (C 1 -C 5) alkylamino group or a bis- [a carboxylic acid (C 1 -C 5) alkyl] amino group; a hydroxyl group Or (C 1 -C 4) an alkoxy group which may be substituted (C 1 -C 4) alkanoylamino group; a phenylamino group which may be substituted with a carbonyloxy group, a sulfonic acid group or an amino group; A sulfonic acid group; a halogen atom or a ureido group, and R ^{1 ()} and R ¹¹ are each independently a hydroxyl group; an amino group; a (C 1 to C 4) alkoxy group; a hydroxyl group or a (C 1 to C 4) alkoxy group An optionally substituted (C1-C4) alkylamino group; a mono- [functional propyloxy (C1-C5) alkyl] amino group or a bis- [functional propyloxy (C1-C5) alkyl] amino group; MONO [S Ho (C 1 through C 5) alkyl] amino group or bis - [Suruho

(C 1 -C 5) alkyl] amino group; substituted by carbonyl group, sulfonic acid group, amino group, hydroxyl group, (C 1 -C 4) alkyl group, (C 1 -C 4) alkoxy group or halogen The trisazo compound or salt thereof according to the above (1) or (2), which is a phenylamino group which may be substituted. 4. In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrogen atom; a hydroxy group; an amino group; a carbonyl group; a (C 1 to C 4) alkyl group, a hydroxy group or 1 to C4) The trisazo compound according to the above (1) or (2), which is a (C1 to C4) alkoxy group or a (C1 to C4) alkanoylamino group which may be substituted by an alkoxy group, or a trisazo compound thereof. salt.

(5) In the general formula (3), R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom; a hydroxyl group; (C 1 -C 4) an alkoxy group or a sulfonic acid group, The trisazo compound or a salt thereof according to 2).

(6) In the general formula (1-1), A represents the general formula (3), the bonding position of A is the 2-position, and two kinds of R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms, and Is a sulfonic acid group, and R ^{1 ()} and R ¹¹ each independently have at least one selected from the group consisting of a hydroxyl group, a hydroxyl group and a sulfonic acid group as a substituent. Or the trisazo compound or salt thereof according to the above (1) or (2), which is a di (C 1 -C 5) alkylamino group.

 (7) The salt of the trisazo compound according to the above (1) or (2), wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an ammonium salt represented by the general formula (4).

X ¹

X ⁴ — N + — X ²

X ³ (4)

(In the formula (4), X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group.)

 (8) An aqueous ink composition containing the trisazo compound or a salt thereof according to any one of the above (1) to (7).

 9. Colored body colored with the aqueous ink composition according to the above (8)

 10. Colored body of the above (9), which is colored by an ink-jet printer.

Hereinafter, the present invention will be described in detail. In R ¹ in the general formula (1-1), examples of the (C ¹ -C 4) alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. Examples of the (C 1 -C 4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.

Examples of the (C 1 -C 4) alkyl group which may be substituted with a hydroxyl group or a (C 1 -C 4) alkoxy group in R ² to R ¹¹ in the general formulas (2) and (3) Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl, 2-ethoxyethyl, n —Propoxyshetyl, isopropoxyshetyl, n-butoxyshetyl, methoxypropyl, ethoxypropyl, n-propoxypropyl pill, isopropoxybutyl, n-propoxybutyl and the like. Examples of the (C 1 -C 4) alkoxy group which may be substituted by a hydroxyl group or a (C 1 -C 4) alkoxy group include methoxy, ethoxy, n_propoxy, isopropoxy, n-butoxy, sec-butoxy Tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, Examples include ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy and the like. Examples of the carboxy mono (C 1 -C 5) alkylamino group include carboxylic acid methylamino, carboxyethylamino, carboxypropylamino, carboxylic acid n-butylamino, carboxy-1-n-benzylamino, and the like. Examples of the carbonyl- (C 1 -C 5) alkyl] amino group include bis- (carbonyloxy) amino, bis- (carbonyloxy) amino, and bis (carboxypropyl) amino. Examples of the (C 1 -C 4) alkylamino group which may be substituted by a hydroxyl group or a (C 1 -C 4) alkoxy group include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, Isoptylamino, N, N-dimethylamino, N, N-getylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino, hydroxyethylamino, 2-hydroxypropylamino, 3-hydroxypropylamino And bis (hydroxyethyl) amino, methoxyethylamino, ethoxyethylamino, bis (methoxyethyl) amino, bis (2-ethoxyxethyl) amino and the like. Examples of the (C 1 -C 4) alkanoylamino group which may be substituted by a hydroxyl group or a (C 1 -C 4) alkoxy group include acetylamino, n-propionylamino, isopropionylamino, hydro Xycetylamino, 2-hydroxy-1-n-propionylamino, 3-hydroxy-1-n-propionylamino, 2-methoxyn-propionylamino, 3-methoxy-n-propionylamino, 2-hydroxyn- Butyrylamino, 3-hydroxy-1-n-butyrylamino, 2-methoxy-n-butylylamino, 3-methoxy-n-butyrylamino, and the like. Examples of the phenylamino group which may be substituted with a sulfoxyl group, a sulfonate group or an amino group include phenylamino, sulfophenylamino, carboxyphenylamino, bis-lipoxyphenylamino, and aminophenyl. Nilamino, diaminophenylamino, diaminosulfophenylamino and the like.

In R ⁵ , R ⁶ , R ^1Q and R ¹¹ in the general formulas (2) and (3), examples of the (Cl-C 4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n Butoxy, sec-butoxy, tert-butoxy and the like. Examples of mono- [sulfo (C1-C5) alkyl] amino groups include sulfomethylamino, sulfoethylamino, 2-sulfopropylamino, 3-sulfopropylamino, sulfo_n-butylamino, Examples of bis- [sulfo (C 1 -C 5) alkyl] amino groups include bis-sulfomethylamino, bis- (sulfoethyl) amino, and bis-sulfo (C 1 -C 5) alkyl] amino group.

(Sulfopropyl) amino and the like.

Preferred R ¹ in the general formula (1-1) is hydrogen, methyl, ethyl, n-propyl, methoxy, ethoxy, n-propoxy and the like, particularly preferably methyl, ethyl, methoxy and ethoxy. Preferred R ² and RR ⁴ in the general formula (2) are each independently hydrogen, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, chlorine, carboxyl, sulfonic acid, hydroxy, amino, carboxymethylamino, Carboxypropylamino, bis-propoxymethylamino, acetylamino, ureido, phenylamino, sulfophenylamino, carboxyphenylamino, dicarboxyphenylamino, etc., and more preferably methyl, methoxy, sulfonic acid , Hydroxy, amino, acetylamino, phenylamino, sulfophenylamino, carboxyphenylamino, and dicarboxyphenylamino. Particularly preferred are amino, hydroxy, sulfonic acid, propyloxyl, acetylamino and phenylamino.

Desirable R ⁷ , R ⁸ , and R ⁹ in the general formula (3) are each independently hydrogen, methyl, methoxy, chlorine, carboxyl, sulfonic acid, hydroxy, amino, carboxymethylamino, carboxypropylamino, or bis-hydroxypropyl. Methylamino, acetylamino, ureido, phenylamino, sulfophenylamino, difluorooxyphenylamino, dicarboxyphenylamino, etc., and more preferably methoxy, sulfonic acid, hydroxy, amino, acetylamino, phenylamino. , Sulfophenylamino, carboxyphenylamino, and dicarboxyphenylamino. Particularly preferred are amino, hydroxy, sulfonic acid, carboxylic acid, acetylamino, and phenylamino.

Preferred R ⁵ , R ⁶ , R ^1Q , and R ¹¹ in formulas (2) and (3) are each independently hydroxy, methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, amino, methylamino, methylamino, propyl Amino, isopropylamino, butylamino, dimethylamino, getylamino, dibupyramino, diisopropylamino, dibutylamino, morpholino, 2-hydroxyhexylamino, bis- (2-hydroxyethyl) amino, 2-hydroxypropylamino Bis (2-hydroxypropyl) amino, Bis (3-hydroxypropyl) amino, Bis (3-hydroxypropyl) amino, 2-ethoxyshethylamino, 2- (2-hydroxyethoxy) ethylamino, 2-Hydoxyshethylmethyl Amino N-(2-Hidokishechiru) Echiruamino, N-(2 —Hydroxypropyl) methylamino, N— (2-Hydroxypropyl) ethylamino, Poweroxymethylamino, 2-Poweroxypropylamino, 3-Poweroxypropylamino, 5-Carboxypentylamino, Bis-propoxymethylamino, 2-sulfoxyshetylamino, acetylamino, phenylamino, sulfophenylamino, carboxyphenylamino, carboxy-hydroxyphenylamino, etc., and more preferably amino, hydroxy, methylamino. , Ethylamino, dimethylamino, getylamino, 2-hydroxyethylamino, bis- (2-hydroxyethyl) amino, 2-hydroxypropylamino, bis (2-hydroxypropyl) amino, 2-hydroxylpoxicetila Mino, 2 sulphoxyshetylamino, su Hofueniruamino, Cal poke Schiff enyl amino, Karupokishi - a hydroxyphenyl § Mino like. Particularly preferred are amino, hydroxy, 2-hydroxyethylamino, bis- (2-hydroxyethyl) amino, 2-hydroxypropylamino, bis- (2-hydroxypropyl) amino, and 2-hydroxylpoxicetil. Amino, is 21-sulfoxyshetylamino. Preferred examples of the compound represented by the general formula (111) or (1-2) include the compounds shown in the following table. However, it is not limited to these. Tables 1 to 22 below show portions corresponding to R ¹ and A in the general formula (1-1). In Tables 1 to 10, A means the formula (2), and in Tables 11 to 22, A means the formula (3).

Tables 1B to 12B below show the portion corresponding to A in the general formula (1-2). In Tables 1B to 12B, -NH-ph-m-S03H represents the following groups.

In Tables 1B to 6B, A means the formula (2), and in Tables 7B to 12B, A means the formula (3). In addition, a in the acronym of the compound No. indicates that the bonding position of A in the general formula (1-1) is the 2-position, and J indicates that the bonding position of A in the general formula (1-1) is 3 It is a place.

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ZC8600 / C00Zdf / X3d contract 00Z OAV 00

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(! Table 9B)

Compound 10 Compound 10

 A A

 No. 11 No. R11

T1701B -NH2 T1801B. "One thigh

1701B -NHC2H40H J1801B -NHC2H40H

 -NHC2H40H T 1802B -NHC2H40H Same as above Same as above

 -NHC2H40H 1802B-HC2H40H 1 N (C2H right) 2 Tl Marauder 1 N (C2H pole) 2 Same as above Same as above

 1 N (C2H machine) 2 J 1803B -N (C2H40H) 2 γ 1704B -NHC2H4C00H T 1804B -NHC2H4C00H Same as above Same as above

J 1704B -NHC2H4COQH J 1804B -NHC2H4C00H γ1705 (one NCCH2) 2 T 1805B -N (CH2COOH) 2 Same as above Same as above

J 1705B-HC2H40H J 1805B -NHC2H40H γ 1706Β -NHC2H4S03H T 1806B -NHCZH4S03H Same as above Same as above

J 1706B-HC2H4S03H J 1806B -NHC2H4S03H

T 1707B '-N (n-Bu) 2 T 1807B -N (n-Bu) 2 Same as above Same as above

1 1707B -NHC2H4C00H J 1807B -NHC2H4C00H

T 1708B -N (n-Bu) 2 T 1808B -N (n-Bu) 2 Same as above Same as above

J 1708B-HC2H4S03H J 1808B-HC2H4S03H

T 1709B -OH T 1809B -OH Same as above Same as above

J 1709B -NHC2H40H J 1809B-HC2H40H

T1710B -0CH3 T1810B .-0CH3 Same as above Same as above

J 1710B -NHC2H40H J 1810B-HC2H40H

T 1711B T1811B

 Same as above

J 1711B HC2H4C00H J 1811B NHC2H4C00H

T1712B T1812B

 Same as above

J 1712B-HC2H4S03H J 1812B-HC2H4S03H

T1713B -NH-ph-m- S03H T1813B -NH-ph-m- S03H Same as above Same as above

J 1713B-HC5H10C00H- J 1813B-HC5H10C00H-

T1714B -NH-ph-m- S03H T1814B -NH-ph-m- S03H Same as above Same as above

1 1714B-HC2H40H J 1814B -NHC2H40H

T1715B T1815B -i | ^{-Q- oH}

 Same as above X300H Same as above 'COOH J 1715B J 1815B

-HC2H40H -NHC2H40H

Physical condition

(¾1 ω o

Salts are salts of inorganic or organic cations. Among them, specific examples of the inorganic salt include an alkali metal salt, an alkaline earth metal salt and an ammonium salt. Preferred inorganic salts are lithium, sodium and potassium salts and an ammonium salt. Examples of the salt of the organic cation include a salt of the compound represented by the above formula (4). However, it is not limited to these.

Examples of the groups represented by X ¹ , X ² , X ³ and X ⁴ in the general formula (4) include, for example, the following.

 Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-tert-butyl and the like.

 Examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, and 2-hydroxybutyl. C1-C4) alkyl groups.

Examples of the hydroxyalkoxyalkyl group include a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, a 3-hydroxyethoxypropyl group, a 2-hydroxyethoxypropyl group, a 4-hydroxyethoxybutyl group, and a 3-hydroxyethoxybutyl group. And a hydroxy (C1-C4) alkoxy (C1-C4) alkyl group such as a 2-hydroxyethoxybutyl group, and among them, a hydroxyethoxy (C1-C4) alkyl group is preferable. Particularly preferred are a hydrogen atom; a methyl group; a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and a 2-hydroxybutyl. A hydroxy mono (C 1 -C 4) alkyl group such as a group; a hydroxyethoxymethyl group, a 2-hydroxyethoxyethyl group, a 3-hydroxyethoxypropyl group, a 2-hydroxyethoxypropyl / group, a 4-hydroxyethoxybutyl group, Examples thereof include a hydroxyethoxy (C 1 -C 4) alkyl group such as a 3-hydroxyethoxybutyl group and a 2-hydroxyethoxybutyl group. Specific examples of the compound of the general formula (4) are shown in (Table 23).

(Table 23)

 ■ y-2 Υ3 V4

 Ρ Ύ 丄, U ·

 4-1 丄 -Γ? Η4ΠΗ -Γ? Η4 · 0Η -Η2Η4ΠΗ

 No no no no ώϋ ^ ΐΙ / ΓΙ ΓΙ ^ λΓΙ

 4-3 H -CH2CH (OH) CH3 -CH2CH (OH) CH3 -CH2CH (0H) CH3

4-4 CH3-CH2CH (0H) CH3-CH2CH (OH) CH3-CH2CH (0H) CH3

4-5 H -C2H40H H -C2H40H

4-6 CH3 -C2H40H H -C2H40H

4-7 H -CH2CH (OH) CH3 H -CH2CH (0H) CH3

4-8 CH3 -CH2CH (0H) CH3 H -CH2CH (0H) CH3

4-9 CH3 -C2H40H CH3 -C2H40H

4-10 CH3-CH2CH (0H) CH3CH3-CH2CH (0H) CH3 The trisazo compound of the present invention represented by the general formula (1-1) can be synthesized, for example, by the following method. The structural formula of the compound in each step is expressed in the form of a free acid.

 That is, the general formula (5)

(Wherein, Y represents a hydrogen atom, a (C1-C4) alkyl group or a halogen atom.) A compound represented by the formula:

(Wherein, R ¹ is hydrogen; (C 1 C 4) alkyl group; (C 1 C 4) alkoxy group). Generated general formula (7)

(Wherein Y has the same meaning as described above), and then diazotized, and then the following general formula (8)

 (In the formula, the bonding position of the amino group is at the 2- or 3-position.) A coupling reaction is performed with the compound represented by the formula: Generated general formula (9)

(In the formula, Υ and R ¹ have the same meaning as described above. The bonding position of the amino group is at the 2- or 3-position.)

Hydrolyzes the disazoic compound represented by the general formula (10)

(In the formula, R ¹ has the same meaning as described above. The bonding position of the amino group is at the 2- or 3-position.) The compound is then diazotized. The diazo compound obtained has the following general formula (11)

(Wherein, R ² and RR ⁴ have the same meanings as described above.)

Or the following general formula (1 2)

(Wherein, R ⁷ and RR ⁹ have the above-mentioned meanings.)

And a coupling reaction.

As the compound represented by the general formula (11), a compound corresponding to each target compound may be used, and specific examples thereof include 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5- Dimethylbenzene, 1-amino-2-methoxy-5-acetylaminobenzene, 1-amino-2-hydroxy-5-methoxybenzene, 1-amino-3-hydroxy-16-methoxybenzene, 1-amino1-2-methoxyethoxy-5- Acetylamino, 1-amino-2-methoxybenzene, 1-amino-2-methylbenzene, 1-amino-2,5-dimethoxybenzene, 1-amino-2,5-diethoxybenzene, 1-amino-1 2 , 5-bis (2-hydroxyethoxy) benzene, 1-amino-2- Methyl-5-acetylaminobenzene, 1-amino-2-methoxy-5-ureidobenzene, 1-amino-2-methyl-5-ureidobenzene, 1-amino-3-methoxybenzene, 1-amino-3-methylbenzene, 1-amino-2- (2'-hydroxyethoxy) -5-methylbenzene, 3-aminobenzoic acid, 2-amino-4-hydroxybenzoic acid, 3-amino-4-monomethylbenzoic acid, 3-amino-4-methoxybenzoic acid, 2,4-Diaminobenzoic acid, 2,4-Diaminobenzenesulfonic acid, 2-Amino-4-acetylaminobenzenesulfonic acid, 3-Aminobenzenephosphonic acid, 4-Methoxy-13-aminophenol, 2, 4 diamino anisol and the like. Preferred are 2-amino-4-hydroxybenzoic acid, 2,4-diaminobenzenesulfonic acid and 2-amino-4-acetylaminobenzenesulfonic acid. These can be used alone or in a mixture of two or more.

 As the compound represented by the general formula (12), a compound corresponding to each target compound may be used, and specific examples include 8-amino-3-naphthalenesulfonic acid and 5-amino-12-naphthalene sulfone. Acid, 8-amino-14-hydroxy-12-naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 6-amino-14-hydroxy-2-naphthalenesulfonic acid, 5- Amino-6-methoxy-2-naphthalenesulfonic acid, 6-amino-2-naphthalenesulfonic acid, 1-amino-8-hydroxy-3,

6-naphthalenedisulfonic acid (H acid), 1-amino-8-hydroxy-4,6-naphthalenedisulfonic acid (K acid), 2-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (2R acid), 6-amino-2-naphthalenesulfonic acid,

7-amino-1-hydroxy-13-naphthalenesulfonic acid (carboxylic acid), 6-amino-1-hydroxy-13-naphthalenesulfonic acid (J-acid), 5-amino-11-hydroxy-13-naphthalenesulfonic acid (M Acid), 8-amino-1-naphthalenesulfonic acid, 8-aminona-2-phthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 6-amino-12-naphthalenesulfonic acid, and the like. Preferably, 8-amino-2-naphthalenesulfonic acid, 6-amino-2-naphthalenesulfonic acid, 7-amino-1-hydroxy-13-naphthalenesulfonic acid (α Acid). These can be used alone or as a mixture of two or more. Further, a mixture of two or more kinds selected from the general formulas (11) and (12) can also be used.

 The following general formula (13) or (14) formed by the above reaction

 Four)

(Wherein, R ¹ to R ⁴ and R ⁷ to R ⁹ have the same meanings as above), and reacting with cyanuric chloride to obtain the following general formula (15) or (16)

 (16)

(Wherein, R ¹ to R ⁴ and R ⁷ to R ⁹ have the above-mentioned meanings). By reacting the obtained compound with alcohols, amines, and phenols respectively corresponding to the target compound, the following general formula (17) or (18), which is a trisazo compound of the present invention, can be obtained.

(Wherein, from R ¹ R ^u have the meanings given above.) Further, after the general formula (9) was Jiazo of, without hydrolyzing the general formula (1 1) or (12) and the coupling Thereafter, the compound is reacted with cyanuric chloride, which is reacted with alcohols, amines and phenols, and then hydrolyzed to obtain the compounds of the general formulas (17) and (18) of the present invention. it can. The compound represented by the general formula (6), the 4-position: ¹ groups substituted 2 Nitorofue Nord and propane sultone N, aprotic polar organic medium, such as N- dimethylformamide, such as sodium hydroxide The reaction is carried out in the presence of an alkali to give 2-nitro (3-sulfopropoxy) benzene in which the R ¹ group is substituted at the 4-position, and then this is dissolved in an aqueous or aqueous organic medium under a catalyst such as palladium carbon. It can be synthesized by an addition-reduction method.

The diazotization of the compounds of the general formula (5) is carried out in a manner known per se, for example in an inorganic acid medium, for example at −5 to 30 ° C., preferably at a temperature of 0 to 10 ° C. It is carried out using a salt, for example, an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the general formula (5) with the compound of the general formula (6) is also carried out under conditions known per se. That is, it is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example, at a temperature of −5 to 30 ° C., preferably 0 to 10 ° C., and at a weakly acidic to slightly alkaline. It is preferably carried out at a weakly acidic to neutral pH, for example, at pH 3 to 7, and the pH value is adjusted by adding a base. The base may be, for example, an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide, an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, an acetate such as sodium acetate, or ammonia or organic amine. Can be used. The compounds of general formulas (5) and (6) are used in approximately stoichiometric amounts.

 The diazotization of the compound of the general formula (7) can also be carried out by a method known per se. For example, diazotization in an inorganic acid medium using, for example, a nitrite, for example, a metal nitrite such as sodium nitrite, at a temperature of -5 to 30 ° (preferably 0 to 20 ° C) The coupling of the diazotized compound of the general formula (7) with the compound of the general formula (8) can also be carried out under conditions known per se, that is, in an aqueous or aqueous organic medium, for example, at 15 to 30 ° C. Advantageously, it is carried out at a temperature of preferably 10 to 25 ° C. and under mildly acidic to alkaline conditions, preferably carried out at a neutral to alkaline pH, for example between pH 7 and 11. Adjustment of this pH value Is carried out by the addition of a base such as an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide, an alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate, Acetates such as sodium acetate, ammonia or organic amines can be used, etc. The compounds of general formulas (7) and (8) are used in almost stoichiometric amounts.

The production of the compound of the general formula (10) by hydrolysis of the disazo compound of the general formula (9) is also carried out by a method known per se. Heating is advantageously carried out in an aqueous medium.For example, sodium hydroxide or potassium hydroxide is added to a reaction solution containing the compound of the general formula (9) to adjust the pH to 9.5 or more. Then, for example, heating to a temperature of 20 to 150 ° C, preferably 30 to 100 ° C It is implemented. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to 11.5. The adjustment of the pH value is carried out by adding a base. As the base, those described above can be used. The diazotization of the hydrolyzed compound of the general formula (10) can be carried out under the same conditions as the diazotization of the compound of the general formula (7). Coupling of the diazotized compound of the general formula (10) with the compound of the general formula (11) or (12) can also be carried out under conditions known per se. The coupling reaction is carried out in an aqueous or aqueous organic medium, for example at a temperature of 0 to 40 ° C., preferably 10 to 30 ° C., at pH 3 to 10, preferably at pH 6 to 8.

 The reaction of the compound of the general formula (13) or (14) with cyanuric chloride is also carried out under conditions known per se. The reaction is carried out in an aqueous or organic medium, for example at 0 to 40 t, preferably at a temperature of 0 to 30 ° C., at ρΗ1 to 7, preferably at pH 3 to 7.

 The reaction of the compound of the formula (15) or (16) with alcohols, amines or phenols is also carried out under conditions known per se. It is carried out in an aqueous or organic medium, for example at a temperature of 20 to 100 ° C., preferably 40 to 90 ° C., at a pH of 3 to 10, preferably at a pH of 4 to 9. The trisazo compound of the present invention represented by the general formula (1-2) can be synthesized, for example, by the following method.

 General formula (5)

(Wherein, Y represents a hydrogen atom, a (C1-C4) alkyl group or a halogen atom). ₀ _ ^-OCOCH ₃

.

 Perform a coupling reaction with OCOCH3 (6B) to obtain the general formula (7B)

(Wherein Y has the same meaning as described above). The obtained compound is diazotized to obtain a compound represented by the general formula (8)

(In the formula, the substitution position of the amino group is at the 2- or 3-position.) Coupling with the compound represented by the general formula (9B)

(In the formula, Y has the same meaning as described above. The substitution position of the amino group is 2- or 3-position.)

To obtain a compound represented by the disazo compound represented by the formula: The obtained compound is hydrolyzed to give a compound of the general formula (10Β)

(In the formula, the substitution position of the amino group is at the 2- or 3-position.) After diazotizing this, the general formula (11)

(Wherein, R ² , R ³ and R ⁴ have the same meanings as described above.)

Or general formula (12)

(Wherein, R ⁷ , R ⁸ , and R ⁹ have the meanings described above.)

To obtain a Trisazoich compound represented by the following general formula (13B) or (14B).

Specific examples of the compound represented by the general formula (11) include: 1-amino-2-methoxy-15-methylbenzene, 1-amino-2,5-dimethylbenzene, 1-amino-2-methoxy-15-methylbenzene Cetylaminobenzene, 1-amino-2-hydroxy-15-methoxybenzene, 1-1-amino-3-hydroxy-16-methoxybenzene, 1-amino-2-methoxyethoxy-5-acetylaminobenzene, 1-amino 1-methoxybenzene, 1-amino-2-methylbenzene, 1-amino-2,5-dimethoxybenzene, 1-amino_2,5-ethoxyethoxy Then, 1-amino-1,2,5-bis (2-hydroxyethoxy) benzene, 1-amino-2-methyl-15-acetylaminobenzene, 1-amino-2-methoxy-5-peridobenzene, 1— 1-amino-5-peridobenzene, 1-amino-3-methoxybenzene, 1-amino-3-methylbenzene, 1-amino-2- (2'-hydroxyethoxy) -1-5-methylbenzene, 3-aminobenzo Acid, 2-amino-4-hydroxybenzoic acid, 3-amino-4-methylbenzoic acid, 3-amino-4-methoxybenzoic acid, 2,4-diaminobenzoic acid, 2,4-diaminobenzenesulfonic acid, 2-amino-4-acetylaminobenzenesulfonic acid, 3-aminobenzenephosphonic acid, 4-methoxy-13-aminophenol, and 2,4-diaminoazole, and the like. Mashiku is 2-Amino-4-hydroxybenzoic acid, 2, 4-di § amino benzene sulfonic acid, 2-amino one 4-§ cetyl § amino benzenesulfonic acid. These can be used alone or in a mixture of two or more.

Specific examples of the compound represented by the general formula (12) include 8-amino-3-naphthylene sulfonic acid, 5-amino-2-naphthylene sulfonic acid, and 8-amino-4 1-naphthylene sulfonic acid. Lensulfonic acid, 8-amino-1-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 6-amino-4-hydroxy_2-naphthalenesulfonic acid, 5-amino-6-methoxy-12-naphthalenesulfonic acid, 6-amino-2-naphthalenesulfonic acid, 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid (H acid), 1-amino-8-hydroxy-1,4,6-naphthalenedisulfonic acid (K acid) , 2-amino-1-hydroxy-3,6-naphthalenedisulfonic acid (2R acid), 6-amino-1-naphthalenesulfonic acid, 7-amino-1-hydroxy-3-naphthalene sulfo Acid (carboxylic acid), 6-amino-1-hydroxy-3-naphthalenesulfonic acid (J acid), 5-amino-1-hydroxy-13-naphthalenesulfonic acid (M acid), 8-amino-1-naphthalenesulfonic acid And 8-amino-2-phthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 6-amino-12-naphthalenesulfonic acid, and the like, preferably 8-amino-2-naphthalenesulfonic acid, 6—Amino 2-naphthalenesulfonic acid and 7-amino-1-hydroxy-3-naphthalenesulfonic acid (T-acid). These can be used alone or as a mixture of two or more. If desired, a mixture of two or more selected from these general formulas (11) and (12) may be used.

 The following general formula (13B) or (14B) obtained by the above coupling reaction

(Wherein, R ² to R ⁴ and R ⁷ to R ⁹ have the same meanings as described above), and reacting cyanuric chloride with a cyanuric chloride represented by the following general formula (15B) or (16B)

(Wherein, R ² to R ⁴ and R ⁷ to R ⁹ have the above-mentioned meanings). By reacting the obtained compound with alcohols, amines and phenols, general formula (17B) or (18B) which is the trisazo compound of the present invention can be obtained.

(Wherein, R ² to R ¹¹ have the above-mentioned meanings.) Further, after diazotizing the general formula (9B), the compound is coupled with the general formula (11) or (12) without hydrolysis. And then reacting with cyanuric chloride, which is reacted with alcohols, amines and phenols and then hydrolyzed to obtain compounds of the general formulas (17B) and (18B) of the present invention. be able to.

The compound represented by the general formula (6B) can be synthesized by the method described in International Publication WO 00/43453, Ex amp 1 e2, Ste ρ1. The diazotization of the compounds of the general formula (5) is carried out in a manner known per se, for example in an inorganic acid medium, for example at a temperature of 15 to 30 ° C., preferably at a temperature of 0 to 10 ° C., for example nitrites, for example. It is carried out using a metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the general formula (5) with the compound of the general formula (6B) is also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of from −5 to 30, preferably from 0 to 10 ° C., under mildly acidic to weakly acidic conditions. It is preferably carried out at a weakly acidic to neutral pH value, for example, pH 3 to 7, and the pH value is adjusted by adding a base. base Examples include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, lithium metal carbonates such as lithium carbonate, sodium carbonate or potassium carbonate, acetates such as sodium acetate, or ammonia or organic amines. Can be used. The compounds of general formulas (5) and (6B) are used in approximately stoichiometric amounts.

 The diazotization of the compounds of the general formula (7B) is also carried out in a manner known per se, for example in an inorganic acid medium, for example at a temperature of -5 to 30 ° C, preferably at a temperature of 0 to 20 ° C, of nitrite, for example nitrous acid. This is carried out using a metal nitrite such as sodium nitrite. The diazotized compound of the general formula (7B) and the coupling of the compound of the general formula (8) are also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of from 15 to 30 ° (preferably at a temperature of from 10 to 25 ° C., under weakly acidic to alkaline conditions. Preferably from neutral to alkaline The pH is adjusted at a pH of, for example, pH 7 to 11. The pH is adjusted by adding a base, such as lithium metal hydroxide such as lithium hydroxide and sodium hydroxide. Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, etc., acetates such as sodium acetate, ammonia or organic amines, etc. The compounds of the general formulas (7B) and (8) have almost stoichiometric amounts. It is used arbitrarily.

The production of the compound of the general formula (10B) by hydrolysis of the compound of the general formula (9B) is also carried out by a method known per se. Heating is preferably carried out in an aqueous medium. For example, sodium hydroxide or potassium hydroxide is added to a reaction solution containing the compound of the general formula (9B) to adjust the pH to 9.5 or more. It is carried out, for example, by heating to a temperature of 20 to 150 ° C, preferably 30 to 100. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to 11.5. The adjustment of the PH value is performed by adding a base. As the base, those described above can be used. The diazotization of the hydrolyzed compound of the general formula (10B) can be carried out under the same conditions as the diazotization of the compound of the general formula (7B). Coupling of the diazotized compound of the general formula (10B) with the compound of the general formula (11) or (12) is also carried out under conditions known per se. It is. It is carried out in an aqueous or aqueous organic medium, for example at a temperature of 0 to 40, preferably 10 to 30 ° C., and at a pH of 3 to 10, preferably at a pH of 6 to 8. The reaction of the compound of the general formula (13B) or (14B) with cyanuric chloride is also carried out under conditions known per se. It is carried out in an aqueous or organic medium, for example at a temperature of 0-40 ° C., preferably 0-30 and at a pH of 1-7, preferably pH 3-7.

 The reaction of the compound of the general formula (15B) or (16B) with alcohols, amines or phenols is also carried out under conditions known per se. The reaction may be carried out in an aqueous or organic medium, for example at a temperature of from 20 to 100 °, preferably of from 40 to 90 and at a pH of from 3 to 10, preferably of from 4 to 9. According to the present invention, the trisazoi conjugate represented by the general formula (1-1) or the general formula (1-2) or a salt thereof (hereinafter, unless otherwise noted, a trisazo compound or a salt thereof is simply referred to as a trisazo compound) After the coupling reaction, it can be isolated in the form of the free acid by addition of a mineral acid. The inorganic salt can be removed by washing the isolated compound with water or acidified water. Next, the acid type dye having a low salt content thus obtained can be neutralized with a desired inorganic or organic base in an aqueous medium to form a solution of the corresponding salt. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, and alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate. And the like. Examples of the organic base include, but are not limited to, amines represented by the above general formula (4), for example, alkanolamines such as jetanolamine and triethanolamine.

 The trisazo compounds of the present invention are remarkably suitable for dyeing natural materials such as paper, cellulose, wool, and leather, and blended products of these and synthetic fiber materials. Remarkably suitable for liquid production.

The reaction solution containing the trisazo compound of the present invention can be used directly for producing a recording ink composition. But first dry it, for example, spray dry Isolate, salt out with inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate, etc., or acid precipitate with mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. It is also possible to take out the trisazo compound of the present invention by carrying out acid precipitation in combination with the above, and then process this into an ink composition.

 Next, the aqueous ink composition of the present invention will be described.

 The aqueous ink composition of the present invention contains water containing 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the trisazo compound of the present invention as a main medium. Composition. The ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 5% by mass of an ink preparation agent.

 The aqueous ink composition of the present invention is obtained by dissolving the trisazo compound of the present invention in water or a water-soluble organic solvent (organic solvent or water containing an organic solvent miscible with water), and adding an ink preparation as necessary. Things. The pH of the aqueous ink composition of the present invention is preferably about 5 to 11. When this water-based ink composition is used as an ink for an ink jet printer, it is preferable to use, as the trisazo compound, one having a low content of inorganic substances such as chlorides and sulfates of metal cations. Is about 1% by mass or less (based on chromogen). In order to produce a trisazo compound having a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a dried product or a wet cake of the trisazo compound of the present invention is stirred in a mixed solvent of alcohol and water such as methanol. Desalination may be performed by a method such as filtration and drying.

Examples of the water-soluble organic solvent that can be used in preparing the aqueous ink composition of the present invention include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butyl. Lactams such as C 1 -C 4 alkanols such as phenol, carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetoamide, 2-pyrrolidone, N-methylpyrrolidin-2-one; Cyclic ureas such as 3-dimethylimidazolidin-1-one or 1,3-dimethylhexahydropyrimid-2-one, acetate Ketones such as ethylene, methylethyl ketone, 2-methyl-2-hydroxypentane-4-one, or cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol; 1,2-propylene glycol; Pyrendalcol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene dalicol, dipropylene glycol, thiodiglycol, Monomers, oligomers or polyalkylene glycols having (C2-C6) alkylene units such as polyethylene glycol and polypropylene glycol or polyols such as thioglycol, glycerin and hexane-1,2,6-triol Le), Of polyhydric alcohols such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, or ethylene glycol monoethyl ether, triethylene glycol monomethyl ether, or triethylene glycol monoethyl ether; C 1 -C 4) alkyl ether, acetylolactone or dimethyl sulfoxide.

Examples of the ink preparation agent include an antiseptic / antifungal agent, a pH adjusting agent, a chelating agent, an antibacterial agent, a water-soluble ultraviolet absorber, a water-soluble polymer compound, a dye dissolving agent, a surfactant and the like. Examples of the antiseptic / antifungal agent include sodium acetic anhydride, sodium sorbate, sodium 2-pyridinethiol-l-oxide, sodium benzoate, sodium pentachlorophenol and the like. As the pH adjuster, any substance can be used as long as it can control the pH of the ink within a range of, for example, 5 to 11 without adversely affecting the ink to be prepared. Examples include alkanolamines such as diethanolamine and triethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium oxide and potassium hydroxide, ammonium hydroxide (ammonia), or lithium carbonate. , Sodium carbonate, carbonate carbonate, etc. Examples of chelating reagents include sodium ethylenediaminetetraacetate, sodium triacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, and sodium peracyl niacetate. Can be Examples of the protective agent include acid sulfite, sodium thiosulfate, ammonium thiodalcholate, diisopropylammonium nitrite, erythritol tetranitrate and dicyclohexylammonium nitrite. Examples of the water-soluble polymer compound include polyvinyl alcohol, a cellulose derivative, polyamine, and polyimine. Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole. Examples of the dye dissolving agent include ε-force prolactam, ethylene carbonate, and urea. Examples of the surfactant include known surfactants such as anion type, cationic type and nonionic type. The aqueous ink composition of the present invention can be obtained by mixing and stirring the above components in any order. The obtained ink composition may be filtered with a membrane filter or the like in order to remove impurities. If desired, a dye other than the trisazo compound of the present invention can be added.

 The colored body of the present invention is colored by the above-described compound of the present invention or the aqueous ink composition containing the same. Examples of the material that can be colored include information transmission sheets such as paper and film, fibers and cloths (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. Examples of the coloring method include a dip dyeing method, a printing method, a printing method such as screen printing, a method using an ink jet printing method, and the like, and a method using an ink jet printing method is preferable.

As the information transmission sheet, a surface-treated sheet, specifically, a sheet in which an ink receiving layer is provided on a base material such as paper, synthetic paper, or film is preferable. In the ink receiving layer, for example, the above base material is impregnated or coated with a cationic polymer, and inorganic fine particles capable of absorbing the dye in the ink such as porous silica, alumina sol and special ceramics are coated with polyvinyl alcohol or the like. It is provided by coating the substrate surface together with a hydrophilic polymer such as polyvinylpyrrolidone. Those provided with such an ink receiving layer are usually referred to as inkjet paper (film), glossy paper (film), etc., for example, Pictorico (made by Asahi Glass Co., Ltd.), color BJ paper, color BJ photo film sheet, Professional Photo Paper (both manufactured by Canon Inc.), Color Image Jet Paper (Sharp Co., Ltd.), Glossy Film for Super Fine, PM Photo Paper (Glossy) (Epson Co., Ltd.), and Picufine (Hitachi Maxell Co., Ltd.). Of course, it can be applied to plain paper.

 The aqueous ink composition of the present invention containing the compound of the present invention is suitable as an ink for printing, copying, marking, writing, drawing, stamping, or a recording method, particularly an ink jet recording method. These inks provide high quality black colorants with high concentrations and good resistance to sunlight, ozone gas and moisture. The trisazo compound of the present invention has higher light resistance and ozone gas resistance especially on paper dedicated to inkjet and glossy paper.

 Since the trisazo compound of the present invention or a salt thereof has a high solubility in water, it does not precipitate or separate during storage. Further, when the aqueous ink composition of the present invention is used for inkjet recording, the injection nozzle is not blocked. The aqueous ink composition of the present invention does not change its physical properties even under relatively long-time recirculation by a continuous ink jet recorder or under intermittent use conditions by an on-demand ink jet recorder. Example

 Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified. Here, the structural formula of the compound in each step is expressed in the form of a free acid.

Example 1

To 100 parts of N, N-dimethylformamide was added 51.0 parts of 2-nitro-4-cresol, 50.0 parts of toluene and 19.5 parts of potassium hydroxide. The mixture was heated to 5 ° C and stirred for 1 hour to distill off water generated by azeotropy with toluene. After the temperature was raised to 130 to 135 ° C, 44.8 parts of propane sultone diluted with 50 parts of N, N-dimethylformamide was added dropwise over about 30 minutes. After reacting at the same temperature for 1 hour, the mixture was cooled to room temperature, added with 150 parts of water, and adjusted to pH 7.5 to 8.5 with a sodium hydroxide solution. This solution was concentrated on a rotary evaporator and transferred to an autoclave, where it contained 50% water and 5% palladium. 1.0 part of carbon was added. After filling with hydrogen gas, the mixture was reacted at 55 to 65 for 2 hours to obtain a solution containing 56.8 parts of the compound of the formula (19).

After dissolving 74.3 parts of the compound of the following formula (20) in 900 parts of water while adjusting the pH to 0.1 to 3.0 with hydrochloric acid, the temperature is adjusted to 5 to 10 ° C, 53.2 parts of 35% hydrochloric acid, 40 parts of 40% 27.0 parts of an aqueous solution of sodium nitrite were added to diazotize.

Then, a solution containing 36.8 parts of the compound of the formula (19) obtained by the above reaction is slowly added dropwise to the diazo suspension of the compound of the formula (20) at a temperature of 0 to 10 ° C. did. After dropping, the pH value is adjusted to 3.0 to 4.0 by adding an aqueous sodium hydroxide solution, and then 1 hour at 5 to 10 ° C and 8 hours at 15 to 25 ° C. The mixture was stirred at 4.0 to complete the coupling reaction, and a reaction solution containing the compound of the following formula (21) was obtained.

Next, the solution containing the compound of the formula (21) obtained above was made weakly alkaline with an aqueous sodium hydroxide solution, and 33.5 parts of a 40% aqueous sodium nitrite solution was added thereto. This solution was added dropwise to a solution of 200 parts of water and 62.6 parts of 35% hydrochloric acid over 30 minutes to diazotize it, and this suspension was treated with 7_amino-1-hydroxynaphthalene-13-sulfonic acid. It was added dropwise to 9 parts of the alkaline aqueous solution at 15 to 30 ° C. During the dropwise addition, the pH value of the solution was maintained at 8.5 to 9.5 with sodium carbonate. After completion of the dropwise addition, the mixture was further stirred at 15 to 30 for 3 hours and at pH 8.5 to 9.5 to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of the following formula (22). In the formula (22), Ts represents a p-toluenesulfonic acid residue.

The reaction solution containing the compound of the formula (22) obtained above was heated to 75 ° C. After the heating, the pH was adjusted to 0.7 with sodium hydroxide, and the pH was maintained at 70 to 75: 0.6 to 10.8 for about 1 hour. Then, the pH was adjusted to about 8.0 with hydrochloric acid, and sodium chloride was added for salting out, followed by filtration and isolation to obtain 94.9 parts of a compound of the formula (23).

After dissolving 8.6 parts of the compound of the formula (23) obtained in the above reaction in 120 parts of water, 2.5 parts of a 40% aqueous sodium nitrite solution was added, and the aqueous solution was added to 50 parts of a 5% aqueous hydrochloric acid solution in 15 parts. The solution was dropped at 30 "C, and the solution was dropped at 15-30 ° C into an aqueous solution of 2.3 parts of 8-amino-12-naphthylene sulfonic acid. During the dropping, the pH value of the coupling solution was dropped. Was maintained at 6.0 to 7.0 with sodium carbonate.After completion of the dropwise addition, the mixture was stirred at 15 to 30 ° C and pH 6.0 to 7.0 for 1 hour. The mixture was stirred at 15 to 30 ° (pH 7.5 to 8.5 for 5 hours to complete the coupling reaction. After that, sodium chloride was added for salting out, followed by filtration. The whole cake was dissolved in 150 parts of water, crystallized by adding 80 parts of 2-propanol, desalted by filtration, and then dried and 9.6 parts of the trisazo compound of the formula (24). Obtained.

After dissolving 5.8 parts of the compound of the formula (24) obtained in the above reaction in 100 parts of water, 1.2 parts of cyanuric chloride was added at 15 to 30 ° C. After the addition, the mixture was stirred at 15 to 30 ° C for 2 hours while maintaining the pH value at 6.0 to 6.7 with sodium carbonate. Next, 2.5 parts of monoethanolamine was added dropwise at 15 to 30 ° C for 30 minutes while maintaining the pH at 8.0 to 9.0 with 5% hydrochloric acid. After dropping, while maintaining the pH value at 8.0 to 9.0 with sodium carbonate, raise the temperature to 85 to 95 ° C for 3 hours at 15 to 30 ° C, and then adjust the PH value with sodium carbonate to 8. The mixture was stirred for 4 hours while maintaining it at 5 to 9.0. After cooling to 20 to 30 ° C, the pH value was adjusted to 5.5 to 6.5 with 35% hydrochloric acid, the insoluble matter was removed by filtration, sodium chloride was added for salting out, and filtration was performed. The total amount of the obtained cake was dissolved in 70 parts of water, crystallized by adding 70 parts of methanol, desalted by filtration, and then dried to obtain the compound of the formula (25) of the present invention. Compound 4.8 of compound No. a 1102) was obtained. The maximum absorption wavelength (Amax) of the compound in water in water was 611 nm.

Example 2

 Monoethanolamine of Example 1 2.5 Tripartazo compound of the formula (26) (Compound No. 1104) was prepared in the same manner as in Example 1 except that 3.5 parts were replaced with 3.5 parts of / 3-alanine 5. 0 parts were obtained. The maximum absorption wavelength of this compound in water was 598 nm.

Example 3

 In the same manner as in Example 1 except that 2.5 parts of taurine was replaced with 4.9 parts of monoethanolamine of Example 1, 5.2 parts of the trisazo compound of the formula (27) (Compound No.r 1106) was added. Obtained. The maximum absorption wavelength of this compound in water was 599 nm.

Example 4

 Except that 35.9 parts of 7-amino-1-hydroxynaphthalene-13-sulfonic acid was changed to 35.9 parts of 6-amino-1-hydroxynaphthalene-3-sulfonic acid in the synthesis step of the compound of the formula (22) in Example 1. In the same manner as in Example 1, a reaction solution containing a disazo compound of the following formula (28) was obtained, and this was hydrolyzed in the same manner as in Example 1 to obtain a disazo compound of the formula (29) 91. 0 parts were obtained.

The following formula (3) was prepared in the same manner as in Example 1 except that 9.1 parts of the disazo compound of the formula (23) in Example 1 was replaced with 9.1 parts of the disazo compound of the formula (29) obtained by the above reaction. 3.6 parts of the trisazo compound of 0) was obtained.

After dissolving 5.8 parts of the compound of the formula (30) obtained in the above reaction in 100 parts of water, 1.4 parts of cyanuric chloride was added at 15 to 30 ° C. After the addition, the mixture was stirred at 15-30 ° C for 2 hours while maintaining the pH value at 6.0-6.7 with sodium carbonate. next Monoethanolamine (2.9 parts) was added dropwise over 30 minutes while maintaining the pH value at 15 to 30 and the pH value at 8.0 to 9.0 with 5% hydrochloric acid. After dropping, the temperature was raised to 40 to 50 ° C, and the pH value was maintained at 8.0 to 9.0 with sodium carbonate for 3 hours.After the temperature was further raised to 85 to 95 ° C, the pH value was increased. The mixture was stirred for 6 hours while maintaining at 8.5 to 9.0 with sodium carbonate. After cooling to 20 to 30 ° C, the pH value was adjusted to 5.5 to 6.5 with 35% hydrochloric acid, the insoluble matter was removed by filtration, sodium chloride was added for salting out, and the mixture was filtered. The total amount of the obtained cake was dissolved in 70 parts of water, crystallized by adding 70 parts of methanol, desalted by filtration, and then dried to obtain a compound 3 of the following formula (31) (Compound No. J 1102). I got 6 copies. The maximum absorption wavelength (Amax) of this compound in water was 623 nm.

Example 5

 The triethazo compound of formula (32) (Compound No. J 1104) was prepared in the same manner as in Example 4, except that 2.9 parts of the monoethanolamine of Example 4 was changed to 4.1 parts of 3-alanine 4.3. Got a part. The maximum absorption wavelength of this compound in water was 610 nm.

Example 6 Monoethanolamine of Example 4 2.9 parts was changed to 5.8 parts of taurine in the same manner as in Example 4 except that trisazo compound of the formula (33) (Compound No. J 1106) was used. Got a part. The maximum absorption wavelength of this compound in water was 610 nm.

Examples 7 to 12

 (A) Creating ink

 Each ink composition of the present invention was prepared by mixing the following components, and each aqueous ink composition for an ink jet was obtained by filtering through a 0.45 m membrane filter. Table 24

 3.0 parts of compound obtained in each of the above Examples

 (Use desalted one)

 Glycerin 5.0 parts

 5.0 copies

 N-methyl-2-pyrrolidone 4.0 parts

 I PA (isopropyl alcohol) 3.0 parts

 Petil carbitol 2.0 parts

 Water + ammonia water 78.0 parts

1 0 0.0 Total In Table 24, as the compounds obtained in the above Examples, as shown in Table 25 below, in Example 7, the compound of the formula (25), in Example 8, the compound of the formula (26), 9, the compound of formula (31) was used in Example 10, the compound of formula (32) was used in Example 11, and the formula (33) was used in Example 12. The pH at the time of ink preparation was adjusted to 9 to 10 with aqueous ammonia. This aqueous ink composition did not undergo sedimentation and separation during storage, and no change in physical properties occurred even after long-term storage.

(B) Ink jet printing

 Using each of the ink compositions obtained above, a special glossy paper A (Canon Professional Photo Paper PR-101) and a special gloss using an ink jet printer (trade name: Can on BJ-S630). Ink jet ed was performed on two types of paper, paper B (E PSON PM photo paper (glossy) KA420 PSK).

 At the time of printing, an image pattern was formed so that the reflection density could have several gradations, and a halftone black print was obtained. Since the gray scale mode is used during printing, the yellow, cyan, and magenta recording liquids other than the black recording liquid are not used in combination in this light-colored portion. Among the test methods described below, in the hue evaluation, which is an item evaluated using a colorimeter, the part with the highest reflection density was used when measuring the L * and a values. Similarly, when measuring the light fastness test and ozone gas fastness test, which are items that are also evaluated using a colorimeter, use the gradation part where the reflection density D value of the printed matter before the test is closest to 1.0. Measurement. For the moisture resistance test and the color rendering test, the whole printed matter was visually evaluated.

 (C) Evaluation of recorded image

 The hue, hue change after xenon lightfastness test (ΔΕ), hue change after ozone gas resistance test (ΔΕ), degree of bleeding by moisture resistance test, color rendering Five points were evaluated. The results are shown in (Table 25). The test method is shown below.

① Hue evaluation The hue of the recorded image was measured using Gretag Macbeth Spectrum Eye (manufactured by GRETAG), and the Δab * value was calculated.

 ② Light fastness test

 Using a Xenon laser meter Ci 4000 (manufactured by AT LAS), the print samples were irradiated for 50 hours at an illuminance of 0.36 WZ square meter. After the test was completed, the color difference (Δ 前後) before and after the test was measured using the above colorimetric system.

 ③Ozone gas resistance test

 Using an ozone weather meter 1 (manufactured by Suga Test Instruments Co., Ltd.), the print sample was left for 2 hours at an ozone concentration of 12 ppm, a humidity of 60% RH, and a temperature of 40 ° C. After the test, the color difference (Δ （) before and after the test was measured using the above colorimetric system.

 湿 Moisture resistance test

 The printed samples were left at 50 ° C and 90% RH for 3 days using a thermo-hygrostat (^ Yogi Sangyo Co., Ltd.), and the dye bleeding before and after the test was visually determined.

 ほ と ん ど Almost no bleeding of dye

 △ Some bleeding of dye is seen

 X There is a considerable amount of dye.

 色 Color rendering test

 The degree of discoloration when viewed under tungsten light was visually determined based on the hue under a standard light source.

 〇 Hue change is small.

 △ Hue change is slightly large.

 X Large hue change. Comparative Example 1

For comparison, C.I.Food B lack 2 (following formula (34)) of an azo dye used as a water-soluble ink jet black dye was used in the same ink composition as in Example 7 to obtain the black ink of the present invention. An ink composition was prepared so that the ink and the optical density matched. The results of the xenon light resistance test, ozone gas resistance test, moisture resistance test and color rendering of the recorded images are shown in Table 25 below.

Comparative Example 2

 Similarly, as a water-soluble inkjet dye for comparison, a dye (the following formula (35)) shown in Ex amp 1 e2 of International Publication WO 00X43451 with the same ink composition as that of Example 7 was used. An ink composition was prepared so that the black ink had the same optical density. The results of the xenon light fastness test, ozone gas fastness test, moisture fastness test, and color rendering of the recorded images are shown in Table 25.

Comparative Example 3

Similarly, as a water-soluble inkjet dye for comparison, a dye (the following formula (36)) shown in Ex amp 1 e3 of International Publication WO0 / 43453 was used with the same ink composition as in Example 7, An ink composition was prepared so that the optical density matched the black ink of the invention. The results of the xenon light fastness test, ozone gas fastness test, moisture fastness test and color rendering of the recorded images are shown in Table 25 below.

(Table 25)

 Hue Light resistance Ozone gas resistance Moisture resistance Color rendering

L * a * b * Color difference (ΔΕ) Color difference (ΔΕ) Example 7 (Equation (25))

 Dedicated glossy paper A 10.7 -8.5 -7.2 2.7 21.1 〇 専 用 Dedicated glossy paper B 10.6 -9.2 -3.5 1.2 18.4 〇 8 Example 8 (Equation (26))

 Dedicated glossy paper A 12.2 -9.6 -6.4 1.9 22.7 〇 〇 Dedicated glossy paper B 13.5 -12.1 -1.7 1.7 15.6 〇 〇 Example 9 (Equation (27))

 Exclusive glossy paper A 10.3 -5.9 -10.7 3.4 25.3 〇 〇 Exclusive glossy paper B 10.0 -8.4 -6.1 1.1 17.7 〇 〇 Example 10 (Equation (3 1))

 Dedicated glossy paper A 8.4 4.0 -14.5 1.2 18.7 〇 〇 Dedicated glossy paper B 10.1 1.8 -5.2 1.5 12.1 1 1 Example 1 1 (Equation (32))

 Special glossy paper A 7.9 1.7 -17.4 1.7 19.0 9.0 専 用 Special glossy paper B 7.7 -1.4 -8.3 1.1 11.1 〇 例 Example 1 2 (Equation (33)

 Dedicated glossy paper A 8.3 2.1 -15.8 0.6 17.2 〇 専 用 Dedicated glossy paper B 7.9 1.0 -8.6 1.9 11.8 例 〇 Comparative example 1 (Equation (34))

 Dedicated glossy paper A 10.8 3.4 -10.2 5.1 48.8 XX Dedicated glossy paper B 8.0 6.2 -6.6 2.5 44.0 XX Comparative example 2 (Equation (3 5))

 Dedicated glossy paper A 9.1 6.8 -14.2 4.5 37.2 〇 X Dedicated glossy paper B 6.2 7.7 -11.3 2.1 30.1 〇 X Comparative example 3 (Equation (36))

Special glossy paper A 9.4 6.8 -14.3 5.2 37.6 〇 X Special glossy paper B 6.4 8.6 -10.6 3.2 30.2 〇 X According to Table 25, the ink composition containing the trisazo compound of the present invention is superior in ozone gas resistance, light resistance, moisture resistance, and color rendering properties as compared with the conventional black dye (Comparative Example). Example 1 B

 After dissolving 74.3 parts of the compound of the following formula (19B) in 900 parts of water while adjusting the pH to 0 to 3.0 with hydrochloric acid, the temperature is adjusted to 5 to 10 ° C, and 53.2 parts of 35% hydrochloric acid, 40 parts of 40% 27.0 parts of an aqueous sodium nitrite solution was added to diazotize the mixture.

(19B)

Next, 44.6 parts of 2,5-bis (2-acetoxchetoxy) aniline dissolved in a solution of 100 parts of water and 15.7 parts of 35% hydrochloric acid was added to the obtained suspension of the diazo compound. The solution was slowly dropped at a temperature of 1010 ° C. After completion of the dropwise addition, the pH value was adjusted to 3.0 to 4.0 by adding an aqueous solution of sodium hydroxide, and then 1 hour at 5 to 10 ° C and 8 hours at 15 to 25 ° C. The mixture was stirred at -4.0 to complete the coupling reaction, and a reaction solution containing the compound of the formula (20B) was obtained.

Next, the solution containing the compound of the formula (20B) obtained above was made weakly alkaline with an aqueous sodium hydroxide solution, and 33.5 parts of a 40% aqueous sodium nitrite solution was added thereto. 30 minutes in a solution of 200 parts of water and 62.6 parts of 35% hydrochloric acid The suspension was added dropwise to an aqueous alkaline solution of 35.9 parts of 7-amino-11-hydroxynaphthalene-3-sulfonic acid at 15-30 "C at 15-30" C. The pH value was maintained at 8.5 to 9.5 with sodium carbonate After completion of the dropwise addition, the mixture was further stirred at 15 to 30 ° C for 3 hours at pH 8.5 to 9.5 to complete the coupling reaction. A reaction solution containing the compound of (21B) was obtained (in the formula (21B), Ts represents a p-toluenesulfonic acid residue)

( ^21Β )

The reaction solution containing the compound of the formula (2IB) obtained above was heated to 75 ° C. After heating, the mixture was adjusted to pH 10.7 with sodium hydroxide, and kept at 70 to 75 ° C and ρΗΙΗΙ.6 to 10.8 for about 1 hour. Thereafter, the pH was adjusted to about 8.0 with hydrochloric acid, salting out was performed by adding sodium chloride, followed by filtration and isolation to obtain 98.1 parts of a compound of the formula (22B).

After dissolving 8.6 parts of the compound of the formula (22B) obtained in the above reaction in 120 parts of water, 2.5 parts of a 40% aqueous sodium nitrite solution was added, and this aqueous solution was added to 50 parts of a 5% aqueous hydrochloric acid solution. The solution was added dropwise at 3030 ° C. to diazotize it, and this was added dropwise to an aqueous solution of 2.3 parts of 8-amino-2-naphthalenesulfonic acid at 15 to 30 ° C. During the dropping, the pH value of the coupling solution was maintained at 6.0 to 7.0 with sodium carbonate. After dropping, stir at 15-30 C, pH 6.0-7.0 for 1 hour, then adjust the pH value to about 8.5 with sodium carbonate, 15-30 ° C, pH 7.5-8.5 For 5 hours to complete the coupling reaction. Then add sodium chloride It was salted out and filtered. The total amount of the obtained cake was dissolved in 150 parts of water, crystallized by adding 80 parts of 2-propanol, desalted by filtration, and then dried to obtain 8.9 parts of the trisazo compound of the formula (23B). Was. The maximum absorption wavelength (Amax) of this compound in water was 598 nm.

After dissolving 5.6 parts of the compound of the formula (23B) obtained in the above reaction in 100 parts of water, 1.2 parts of cyanuric chloride was added at 15 to 3O. After the addition, the mixture was stirred at 15 to 30 ° C for 2 hours while maintaining the pH value at 6.0 to 6.7 with sodium carbonate. Next, 2.5 parts of monoethanolamine was added dropwise over 30 minutes while maintaining the pH value at 8.0 to 9.0 with 5% hydrochloric acid at 15 to 30 °. While maintaining the temperature at 8.0 to 9.0 with sodium, raise the temperature to 85 to 95 ° C for 3 hours at 15 to 30 ° C, and then maintain the pH at 8.5 to 9.0 with sodium carbonate. After cooling to 20 to 30 ° C, the pH was adjusted to 5.5 to 6.5 with 35% hydrochloric acid, the insoluble matter was removed by filtration, and sodium chloride was added to add salt. The whole amount of the obtained cake was dissolved in 70 parts of water, crystallized by adding 70 parts of methanol, desalted by filtration, and then dried to obtain the formula (24B) of the present invention. 4.8 parts of the compound (Compound No. r 1302 B) were obtained, and the maximum absorption wavelength (Amax) in water of this compound was 632 nm.

Example 2B Example IB The procedure of Example 1B was repeated except that 2.3 parts of 8-amino-2-naphthalenesulfonic acid was replaced by 1.9 parts of 2,4-diaminobenzenesulfonic acid in the synthesis of the trisazo compound of formula (23B). In a similar manner, 8.4 parts of the trisazo compound of the formula (25B) was obtained. The maximum absorption wavelength of this compound in water was 597 nm.

After dissolving 5.4 parts of the compound of the formula (25B) obtained in the above reaction in 100 parts of water, 1.0 part of cyanuric chloride was added at 15 to 30 ° C. After the addition, the mixture was stirred for 15 to 30 hours while maintaining the pH value at 4.0 to 5.0 with sodium carbonate. Next, 2.0 to 15 parts of monoethanolamine were added. C. The solution was added dropwise over 30 minutes while maintaining the pH value at 8.0 to 9.0 with 5% hydrochloric acid. After dropping, while maintaining the pH value at 8.0 to 9.0 with sodium carbonate, raise the temperature to 85 to 95 ° C for 2 hours at 15 to 30 ° C, and then adjust the pH value with sodium carbonate. The mixture was stirred for 4 hours while maintaining it at 5 to 9.0. After cooling to 20 to 30 ° C, the pH value was adjusted to 5.5 to 6.5 with 35% hydrochloric acid, the insoluble matter was removed by filtration, sodium chloride was added for salting out, and the mixture was filtered. The whole amount of the obtained cake was dissolved in 70 parts of water, crystallized by adding 70 parts of methanol, desalted by filtration, and then dried to dry the compound of the formula (26B) of the present invention (Compound No. r502B). ) And Formula (27B) (Compound No. 515B) to give 4.2 parts. The maximum absorption wavelength (Amax) of this mixture in water was 612 nm.

Example 3 B

 Monoethanolamine of Example 1B 2.5 g of glycine was replaced by 3.0 parts in the same manner as in Example 1B, except that trisazolone of the formula (28B) (compound No. r 1316 B) of the present invention was used. Compound 4.8 was obtained. The maximum absorption wavelength of this compound in water was 608 nm.

Example 4B

 Monoethanolamine of Example 1B 2.5 In the same manner as in Example 1B except that 3.5 parts was replaced by 3.5 parts of 3-alanine, the formula (29B) of the present invention (compound No. rl304B 5.4 parts of the trisazo compound of formula (1). The maximum absorption wavelength of this compound in water was 612 nm.

Example 5 B

 Monoethanolamine of Example 1 2.5 The trisazo compound of the formula (30B) (Compound No. r 1306B) of the present invention was prepared in the same manner as in Example 1 except that 4.9 parts of taurine was used instead of 5.2 parts. Got a part. The maximum absorption wavelength of this compound in water was 612 nm.

Example 6 B

 In the synthesis stage of the compound of the formula (2 IB) of Example IB 7-amino-1-hydroxynaphthalene-13-sulfonic acid 35.9 9 parts were replaced with 6-amino-11-hydroxysinaphthalene-13-sulfonic acid 35. A reaction solution containing the disazo compound of the formula (31B) was obtained in the same manner as in Example 1B except that the amount was 9 parts.

Take 1/15 of the reaction solution containing the compound of the formula (31B) obtained in the above reaction, add 2.5 parts of a 40% aqueous sodium nitrite solution, and add this aqueous solution to 50 parts of a 5% aqueous hydrochloric acid solution in 15 to 15 parts. The solution was added dropwise at 30 ° C to diazotize it, and this was added dropwise to an aqueous solution of 2.3 parts of 8-amino-2-naphthalenesulfonic acid at 15 to 30 ° C. During the dropwise addition, the pH value of the coupling solution was maintained at 6.0 to 7.0 with sodium carbonate. After dropping, stir at 15-30 ° C, pH 6.0-7.0 for 1 hour, then adjust the pH value to about 8.5 with sodium carbonate, 15-30 ° C, pH 7.5-8 .5 at 5 o'clock The mixture was stirred for a while to complete the coupling reaction. Thereafter, sodium chloride was added thereto, salted out, and filtered to obtain a trisazo compound of the formula (32B).

After dissolving the whole amount of the compound of the formula (32B) obtained in the above reaction in 100 parts of water, 1.2 parts of chlorinated chloride was added at 15 to 30 ° C. After the addition, the mixture was stirred for 2 to 30 hours while maintaining the pH value at 6.0 to 6.7 with sodium carbonate. Next, 2.5 parts of monoethanolamine were added with 15 to 30 and the pH value was adjusted with 8.0% with 5% hydrochloric acid.

The solution was dropped in 30 minutes while maintaining the temperature at 9.0. After dropping, the temperature was raised to 85-95 at 15-30 for 3 hours while maintaining the pH value at 8.0-9.0 with sodium carbonate, and the pH value was adjusted to 8.5-9.0 with sodium carbonate. While stirring at for 4 hours. Next, after cooling to 70-75 ° C, adjust the pH value with sodium hydroxide to 10.5-

The mixture was stirred at the same temperature for 1 hour while maintaining the temperature at 10.8. After cooling to 20-30,

After adjusting the 11 value to 5.5 to 6.5 with 35% hydrochloric acid, the insoluble matter was removed by filtration, sodium chloride was added for salting out, and the mixture was filtered. The total amount of the obtained cake was dissolved in 80 parts of water, crystallized by adding 60 parts of methanol, desalted by filtration, and then dried to form the compound of formula (33B) (Compound No. J 1302B) of the present invention. 4.0 parts of the compound were obtained. The maximum absorption wavelength (Amax) of this compound in water was 625 nm.

Example 7B Monoethanolamine of Example 6B In the same manner as in Example 6B except that 3.5 parts of -alanine was used instead of 2.5 parts of the formula (34B) of the present invention (compound No. J 1304B). 4.9 parts of the trisazo compound was obtained. The maximum absorption wavelength of this compound in water was 624 nm.

(34B)

Example 8 B to l 2 B

 (A) Creating ink

 An ink composition was prepared by mixing the following components, and filtered through a membrane filter of No. 1 to obtain an aqueous ink composition of the present invention for inkjet. Table 14B

 3.0 parts of compound obtained in each of the above Examples

 (Use desalted one)

 Glycerin 50 parts

 50 copies

 N-methyl_2-pyrrolidone 40 parts

 I PA (isopropyl alcohol) 30 parts

 Petil carbitol 20 parts

 Water + ammonia water 780 parts

In the total 100 parts of Table 14B, as the compound obtained in the above example, as shown in Table (15B) below, the compound of formula (24B) was used in Example 8B, and the compound of formula (2B) was used in Example 9B. The compound of formula (30B) was used in Example 10B, the compound of formula (33) was used in Example 11B, and the compound of formula (34B) was used in Example 12B. The pH during ink preparation was adjusted to 9 to 10 with aqueous ammonia. This aqueous ink composition did not undergo sedimentation and separation during storage, and did not change in physical properties even after long-term storage.

(B) Ink jet printing

 Using the respective ink compositions obtained above, a special glossy paper A (Professional Photo Paper PR-101) and a special glossy paper were printed by an ink jet printer (trade name: Can on BJ-S630). Ink jet recording was performed on two types of paper, B (E PSON PM photo paper (glossy) KA420 P SK).

 Printing is done using Photoshop (image retouching software from Adobe) so that the print density can be obtained in six gradations of 100%, 90%, 80%, 70%, 60% and 50%. Printing was performed to obtain a halftone black print. During printing, the sagging scale mode is used, so in this light-colored portion, yellow, cyan, and magenta recording liquids other than black recording liquid are not used in combination. Among the test methods described below, in the hue evaluation, which is an item evaluated using a colorimeter, the part with the highest print density of 100% was used when measuring the L * and color values. Similarly, when measuring the light fastness test and ozone gas fastness test, which are items to be evaluated using a colorimeter, the reflection density D value of the printed matter before the test is 1.0 out of these 6 levels of gradation. The measurement was performed using the tone portion closest to. In the moisture resistance test and the color rendering test, the entire printed matter having six gradations was visually evaluated.

 [0097]

 (C) Evaluation of recorded image

Regarding the image recorded by the aqueous ink composition of the present invention, the hue, the hue change after the xenon light fastness test (ΔΕ), the hue change after the ozone gas fastness test (ΔΕ), the degree of bleeding by the moisture fastness test, the color rendering Five points were evaluated. The results are shown in (Table 15B). The test method is shown below. ① Hue evaluation

 The hue of the recorded image was measured using GretagMacbethSpSpecroEye (manufactured by GRETAG), and the ΙΛab * value was calculated.

 ② Light fastness test

 Using a Xenon Zeaome Ichiichi C 14000 (AT LAS), the print samples were irradiated for 50 hours at 0.36 WZ square meter illuminance. After the test was completed, the color difference (Δ 前後) before and after the test was measured using the above colorimetric system.

 ③Ozone gas resistance test

 Using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.), the print sample was left at an ozone concentration of 12 ppm, a humidity of 60% RH and a temperature of 40 ° C. for 2 hours. After the test, the color difference (Δ （) before and after the test was measured using the above colorimetric system.

 湿 Moisture resistance test

 The printed sample was allowed to stand at 50 ° C. and 90% RH for 3 days using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.), and bleeding of the dye before and after the test was visually determined.

 ほ と ん ど Almost no bleeding of dye

 △ Some bleeding of dye is seen

 X Dye bleeding is noticeable.

 色 Color rendering test

 The degree of discoloration when viewed under tungsten light was visually determined based on the hue under a standard light source.

 〇 Hue change is small.

 △ Hue change is slightly large.

 X Large hue change. Comparative Example 1 B

For comparison, C.I.FoodBlack 2 (the following formula (34)) of an azo-based dye used as a black dye for a water-soluble ink jet was obtained by using the same ink composition as in Example 8B. The ink composition is adjusted so that the optical density matches the black ink of the present invention. Two

Was prepared. The results of the xenon light resistance test, ozone gas resistance test, moisture resistance test and color rendering of the recorded images are shown in Table 15B.

Comparative Example 2 B

 Similarly, as a water-soluble inkjet dye for comparison, a dye (the following formula (35)) shown in Ex amp 1 e2 of International Publication WO 00/43451 with the same ink composition as that of Example 8B was used. An ink composition was prepared so that the black ink of the present invention and the optical density matched. The results of the xenon light fastness test, ozone gas fastness test, moisture fastness test and color rendering of the recorded images are shown in Table 15B.

Comparative Example 3 B

Similarly, as a water-soluble inkjet dye for comparison, a dye (the following formula (36)) shown in Ex amp 1 e3 of International Publication WO0 / 43453 was used with an ink composition similar to that of Example 8B, An ink composition was prepared so that the black ink of the present invention and the optical density matched. The results of the xenon light fastness test, ozone gas fastness test, moisture fastness test and color rendering of the recorded images are shown in Table 15B.

. 5 B)

 Hue Light resistance Ozone gas resistance Moisture resistance Color rendering L * a * b * Color difference (ΔΕ) Color difference (ΔΕ) Example 8B (Equation (24B))

 Special glossy paper A 11.8 -10.7 -2.5 2.4 18.9

 Special glossy paper B 13.4 -15.4 1.4 1.7 12.6

Example 9B (Formula (29B))

 Special glossy paper A 9.6 -8.8 -7.9 5.8 26.1

 Special glossy paper B 10.7 -12.1 -1.4 1.2 14.0

Example 10 B (Equation (30 B)

 Special glossy paper A 12.1 -9.7 -5.5 2.1 19.9

 Special glossy paper B 12.8 -12.1 -1.4 0.9 12.5

Example 11 B (Equation (33 B))

 Special glossy paper A 7.3 0.9 -13.6 3.4 23.6

 Special glossy paper B 7.6 -0.2 -8.9 1.3 15.2

Example 12B (Equation (34B))

 Special glossy paper A 7.6 0.8 -17.5 5.6 27.3

 Special glossy paper B 7.1 -0.1 -10.1 1.1 12.4

 〇〇〇〇〇〇〇〇〇〇〇 〇〇〇 XX Comparative Example 1 B (Equation (34))

 Special glossy paper A 10.4 3.5 -10.2 6.5 46.6

 Special glossy paper B 8.1 6.4 -6.6 4.3 43.0 〇〇〇〇〇〇〇〇〇〇 X X X X X X Comparative example 2 B (Equation (3 5))

 Special glossy paper A 8.6 7.0 -13.9 6.4 34.3

 Special glossy paper B 6.1 7.6 -11.0 3.6 27.4

Comparative Example 3B (Equation (36))

 Special glossy paper A 9.2 7.1 -14.3 7.2 34.2

 Special glossy paper B 6.2 8.6 -10.6 5.3 27.8

From Table 15B, the ink composition containing the trisazo compound of the present invention is superior to the conventional black dye (Comparative Example) in ozone gas resistance, light resistance, moisture resistance, and color rendering. Industrial applicability Since the trisazo compound of the present invention is excellent in water solubility, the trisazo compound has good filterability by a membrane filter in the process of producing an ink composition, and also has excellent storage liquid storage stability and ejection stability. In addition, the ink composition of the present invention containing the trisazo compound does not have crystallization, physical property change, color change, etc. after storage for a long period of time, and has good storage stability. Further, the black ink liquid for recording containing the trisazo compound of the present invention is used for ink jet recording and writing implements, and has a high print density of a recorded image when recorded on plain paper and paper dedicated to ink jet, and further has an ozone gas resistance. Excellent in light resistance, light fastness, moisture fastness and color rendering. When used with magenta, cyan and yellow dyes, full-color ink jet recording with excellent light fastness and water fastness is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for ink jet recording.

Claims

The scope of the claims

 1. A trisazo compound represented by the following general formula (1-1) or (1-2) or a salt thereof

(Wherein, R ¹ is hydrogen; (C ¹ -C 4) an alkyl group; (C ¹ -C 4) an alkoxy group; A represents the general formula (2) or the general formula (3); Second or third place.)

(In the formula (2), R ² to R ⁶ represent an arbitrary substituent.)

(In the formula (3), R ⁷ to R ¹¹ represent an arbitrary substituent.)

2. R ² , R ³ , R ^{4 of the} general formula (2) or R ⁷ , R ⁸ , R ^{9 of the} general formula (3) are each independently a hydrogen atom; a hydroxyl group; an amino group; An unsubstituted or substituted (C 1 -C 4) alkyl group having at least one substituent selected from the group consisting of a hydroxyl group and a (C 1-(: 4) alkoxy group; (C 1 -C 4) alkoxy group having at least one substituent selected from the group consisting of hydroxyl group and (C 1 -C 4) alkoxy group; unsubstituted or substituted (C 1 -C 4) alkyl as a substituent Group, unsubstituted or substituted (C1-C4) mono- or disubstituted amino group substituted by one or two selected from the group consisting of alkanoyl group, unsubstituted or substituted phenyl group

(Provided that the substituent on the substituted alkyl group or the substituted alkanol group is at least one selected from the group consisting of a hydroxyl group, a (C1-C4) alkoxy group and a carbonyl group, and the substituent on the substituted phenyl group Is at least one member selected from the group consisting of a sulfoxyl group, a sulfonate group and an amino group); a sulfonic acid group; a halogen atom or a peridode group, and R ⁵ , R ⁶ of the general formula (2) or the general formula (3 R ^1Q and R ¹¹ independently represent a hydroxyl group; an amino group; a (C 1 -C 4) alkoxy group; as a substituent, an unsubstituted or substituted (C 1 -C 5) alkyl group, an unsubstituted or substituted ( C1-C4) mono- or di-substituted amino group (s) substituted with one or two selected from the group consisting of alkanoyl groups, unsubstituted or substituted phenyl groups (provided that a substituted alkyl group or The substituent on the phenyl group is at least one selected from the group consisting of a hydroxyl group, a sulfonic acid group, a (C1-C4) alkoxy group and a carbonyl group, and the substituent on the substituted phenyl group is a carboxyl group. A sulfonic acid group, an amino group, a hydroxyl group, (C 1 -C 4) an alkyl group, (C 1 -C 4) an alkoxy group or at least one selected from a halogen group. Item 3. The trisazo compound or a salt thereof according to item 1.

3. —In formula (2), R ² , R ³ , and R ⁴ are each independently substituted with a hydrogen atom; a hydroxy group; an amino group; a carbonyl group; a hydroxyl group or a (C1-C4) alkoxy group. (C 1 -C 4) alkyl group; may be substituted by a hydroxyl group or a (C 1 -C 4) alkoxy group (C 1 -C 4) alkoxy group; mono- or di (C 1 -C 4) alkylamino group optionally substituted by hydroxyl group or (C 1 -C 4) alkoxy group; carboxy- (C 1 -C 5) An alkylamino group or a bis- [caproloxy (C1-C5) alkyl] amino group; a (C1-C4) alkanoylamino group which may be substituted by a hydroxyl group or a (C1-C4) alkoxy group; A phenylamino group which may be substituted with a sulfoxyl group, a sulfonic acid group or an amino group; a sulfonic acid group; a halogen atom or a peridode group, wherein R ⁵ and R ⁶ are each independently a hydroxyl group; an amino group; To C4) an alkoxy group; a hydroxyl group or a (C1 to C4) alkylamino group which may be substituted by an (C1 to C4) alkoxy group; ) Alkyl] amino group or bis- [caproloxy (C1-C5) alkyl] amino group; mono [sulfo (C1-C5) alkyl] amino group or bis- [sulfo (C1-C5) [Alkyl] amino group; phenyloxyl group, sulfonic acid group, amino group, hydroxyl group, (C1-C4) alkyl group, (C1-C4) alkoxy group or phenylamino group which may be substituted with halogen. In the general formula (3), R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom; a hydroxy group; an amino group; a carbonyl group; a hydroxyl group or a (C1 to C4) alkoxy group. Good (C 1 -C 4) alkyl group; substituted by a hydroxyl group or (C 1 -C 4) alkoxy group (C 1 -C 4) alkoxy group; hydroxyl group or (C 1 -C 4) Depending on the Coxy group (C 1 -C 4) alkylamino group which may be substituted; Roxy (C 1 -C 5) alkylamino group or bis [carboxy (C 1 -C 5) alkyl] amino group; hydroxyl group or (C 1) To C4) optionally substituted by an alkoxy group (C1 to C4) alkanoylamino group; phenylamino group optionally substituted by a lipoxyl group, a sulfonic acid group or an amino group; a sulfonic acid group A halogen atom or a ureido group, R ^{1 ()} and R ¹¹ are each independently a hydroxyl group; an amino group; a (C 1 -C 4) alkoxy group; a hydroxyl group or a (C 1 -C 4) alkoxy group (C 1 -C 4) alkylamino group; mono [C-Roxy (C 1 -C 5) Alkyl] amino group or bis- [carboxy- (C1-C5) alkyl] amino group; mono- [sulfo (C1-C5) alkyl] amino group or bis- [sulfo- (C1-C5) alkyl] amino A phenylamino group which may be substituted by a carbonyl group, a sulfonic acid group, an amino group, a hydroxyl group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group or a halogen; 3. The trisazo compound or a salt thereof according to item 1 or 2 above.

4. In the general formula (2), R ² , R ³ and R ⁴ each independently represent a hydrogen atom; a hydroxy group; an amino group; a carboxyl group; a (C 1 -C 4) alkyl group, a hydroxy group or a (C 1 To C4) a trisazo compound according to claim 1 or 2, wherein the compound is a (C1 to C4) alkoxy group or a (C1 to C4) alkanoylamino group which may be substituted by an alkoxy group. Or its salt.

5. In the general formula (3), R ⁷ , R ⁸ , and R ⁹ are each independently a hydrogen atom; a hydroxyl group; a (C 1 -C 4) alkoxy group or a sulfonic acid group. 3. The trisazo compound or a salt thereof according to item 1 or 2.

6. In the general formula (111), A represents the general formula (3), the bonding position of A is the second position, two kinds of R ⁷ and RR ⁹ are hydrogen atoms, and the other one is R ^1Q and R ¹¹ each independently represent a mono or di (C 1 to C 1 to C ¹¹⁾ group having at least one substituent selected from the group consisting of a hydroxyl group, a carboxyl group and a sulfonic acid group. C5) The trisazo compound or a salt thereof according to claim 2, which is an alkylamino group.

 7. The salt of the trisazo compound according to claim 1 or 2, wherein the salt is a lithium salt, a sodium salt, a potassium salt, an ammonium salt or an ammonium salt represented by the general formula (4).

X ¹

X ^4- N + 1 X ²

X ³ (4)

(In the formula (4), X ¹ , X ² , X ³ and X ⁴ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group.)

8. An aqueous ink composition comprising the trisazo compound or a salt thereof according to any one of claims 1 to 7.

 9. A colored body colored with the aqueous ink composition according to claim 8.

 10. The colored body according to claim 9, wherein the coloring is performed by an ink-jet printing.