JP2002327131A - New compound, pigment, ink, ink for inkjet and inkjet- recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound excellent printing properties and having favorable color tone and a low degree of dependence on paper, excellent in water resistance and image storability such as light resistance, dark heat storability, and ozone resistance and capable of presenting a high-density black color, a new dye containing the compound, an ink and an inkjet printing ink containing the dyes and an inkjet-recording method using the dye. SOLUTION: This invention relates to the compound represented by general formula (I) (wherein, A and B each independently represents an univalent heterocyclic group bonded to an azo group by a carbon atom of the univalent heterocyclic group; m and n each independently represents one of 0 and 1; M represents a hydrogen atom and an univalent positive ion, with the proviso that A and B are not each simultaneously 1H-pyrazol-3-yl), the dye comprising the compound, the ink and the inkjet printing ink containing the dyes and the inkjet recording method for carrying out recording by using the ink for inkjet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound of a bis-type azo dye exhibiting black, a dye containing the compound, an ink containing the dye and an ink-jet ink, and an ink-jet ink. It relates to the ink jet recording method used.

[0002]

2. Description of the Related Art Dyes exhibiting black are used not only for printing character information but also as black plates in color images. However, the development of a neutral black dye has many technical difficulties. Although a great deal of research and development has been carried out, few of them have sufficient performance at present. For this reason, blacks are formed by mixing a plurality of dyes of various hues, but the development of dyes that exhibit a high-concentration neutral black by itself is the technology that is currently most strongly demanded. It is an issue.

In recent years, with the spread of ink jet printers, black pigments have become more important than ever.
In an ink jet printer, the frequency of printing character information is extremely high as compared with a pictorial printer of another type. Therefore, as a black pigment used in an ink jet printer, there is a problem that the required performance must be satisfied both when used in a black image portion of image information and when used in a character information portion. is there.

The performance required of the black pigment is as follows:
High neutral density black color, excellent ink suitability and ink stability, image fastness (light,
Heat, atmospheric humidity, chemicals, air, various gases in the air,
(Fastness to water and friction), little change in hue depending on the medium (paper) to be printed, excellent dyeability in receiving paper, easy synthesis and low cost, And harmless to the skin.

Conventionally, bis-type azo dyes have been proposed as black dyes, but A and B of the general formula (I) according to the present invention.
Wherein the partial structures corresponding to both are heterocycles,
Until now, with few exceptions. Known black pigments of bisazo type have low concentration (due to low molecular extinction coefficient, which is the basic physical property value of the dye), and neutral black hue (absorption waveform is broad, and light in the visible region is evenly distributed. Absorptive) and poor image fastness. In addition, some black pigments have a structure having a harmful chromium ion in the molecule, which poses a problem in safety for humans and animals.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a novel compound which is neutral at high concentration, exhibits black without color, satisfies various performances required for pigments, inks, and inkjet inks, is inexpensive, and is easy to synthesize. The purpose is to provide. In addition, the printing performance is excellent, the color tone is also preferable, the paper dependence is low, the bleeding does not occur, the water resistance is excellent, the light resistance, the dark heat preservability, and the image preservability such as the ozone resistance are excellent. It is an object of the present invention to provide a novel dye containing the compound, and an ink and an inkjet ink containing the dye, which can exhibit high-concentration black. Still another object of the present invention is to provide an ink-jet recording method which provides a black image having excellent image performance by using the ink-jet ink.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on bis-type azo dyes having a heterocyclic structure, which is a novel structure which has not been known, and show that they have excellent performance as black dyes. The inventors have found a novel compound, a dye containing the compound, an ink containing the dye and an inkjet ink, and an inkjet recording method using the inkjet ink, thereby completing the present invention. Therefore, means for solving the above-mentioned problems are as follows. <1> A compound represented by the following general formula (I).

[0008]

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In the general formula (I), A and B are
Each independently represents a monovalent heterocyclic group bonded to the azo group by a carbon atom. m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are not simultaneously 1H-pyrazol-3-yl.

<2> A dye characterized by containing a compound represented by the following general formula (I).

[0011]

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In the general formula (I), A and B are
Each independently represents a monovalent heterocyclic group bonded to the azo group by a carbon atom. m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are not simultaneously 1H-pyrazol-3-yl.

<3> An ink containing the dye described in <2>. <4> An inkjet ink containing the dye described in <2>. <5> An ink jet recording method characterized by performing recording using the ink for ink jet described in <4>.

<5> A compound represented by the following formula (II-1) or (II-2).

[0015]

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The general formula (II-1) and the general formula (II-
In 2), M ¹ and M ² represent a metal ion. Q ¹ and Q ² are an atomic group forming a heterocyclic group represented by A in the following general formula (I). L represents a ligand coordinated to the metal ion. z represents an integer of 0 or more, and is determined to be a unique number by a metal ion. m and n each independently represent 0 or 1. M is
Represents a hydrogen atom or a monovalent cation. B represents a monovalent heterocyclic group bonded to the azo group via a carbon atom.

[0017]

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In the general formula (I), A and B are
Each independently represents a monovalent heterocyclic group bonded to the azo group by a carbon atom. m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are not simultaneously 1H-pyrazol-3-yl.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compounds, dyes, inks, ink-jet inks and ink-jet recording methods of the present invention will be described in detail. Here, the novel compound of the present invention will be described first.

(New Compound) The novel compound of the present invention is represented by the following general formula (I). <Compound represented by Formula (I)>

[0021]

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In the general formula (I), A and B are
Each independently represents a monovalent heterocyclic group bonded to the azo group by a carbon atom. However, A and B are not simultaneously 1H-pyrazol-3-yl. The monovalent heterocyclic group represented by A is preferably a 5- or 6-membered heterocyclic ring having at least one heteroatom selected from an oxygen atom, a sulfur atom and an oxygen atom in the ring. Among them, from the viewpoint of the stability of the diazonium salt, an aromatic hetero ring is more preferable, and a hetero ring having 2 to 30 carbon atoms is more preferable. The monovalent heterocyclic group represented by A may be further condensed with another ring, and among the condensed ones, a condensed 5- or 6-membered ring is preferable.

The monovalent heterocyclic group represented by A is preferably derived from a diazo component. Here, the diazo component is a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent into a diazo compound, and performing a diazo coupling reaction with a coupler, and is frequently used in the field of azo dyes. This is the concept used. In other words, in an amino-substituted heterocyclic compound capable of a diazotization reaction, it refers to a substituent in which an amino group has been removed to form a monovalent group.

On the other hand, as the monovalent heterocyclic group represented by B, a monovalent heterocyclic group having at least one heteroatom selected from an oxygen atom, a sulfur atom and an oxygen atom in the ring can be used.
Membered or 6-membered heterocycles are preferred. Among them, an aromatic hetero ring is more preferable, and the hetero ring has 2 to 30 carbon atoms.
Are more preferred. The monovalent heterocyclic group represented by B may be further condensed with another ring, and among the condensed ones, a condensed 5- or 6-membered ring is preferable.

The monovalent heterocyclic group represented by B is preferably derived from a coupler component. Here, the coupler component is a partial structure derived from a coupler compound which reacts with a diazonium salt to give an azo dye.
This is a concept frequently used in the field of azo dyes.

In the general formula (I), A and B
The heterocyclic group represented by may further have a substituent, and in this case, the substituents described below are preferable. For example, halogen atom, alkyl group (including cycloalkyl group and bicycloalkyl group), alkenyl group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group Group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group,
An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group,
Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxy Examples include a carbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl and heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

As the halogen atom, for example, a chlorine atom, a bromine atom and an iodine atom are preferable.

Examples of the alkyl group include a linear, branched or cyclic substituted or unsubstituted alkyl group, and in addition to the alkyl group, a cycloalkyl group, a bicycloalkyl group, a tricyclo structure having many ring structures, and the like. included.

Among the above alkyl groups, those having 1 to 30 carbon atoms
(E.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, and 2-ethylhexyl) are preferred. . Among the above cycloalkyl groups, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (for example, cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group)
Is preferred. Among the bicycloalkyl groups, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms (for example, bicyclo [1, 2 ,
2] heptane-2-yl and bicyclo [2,2,2] octan-3-yl group) are preferred. An alkyl group in a substituent described below (for example, an alkyl group of an alkylthio group) also represents an alkyl group having such a concept.

Examples of the alkenyl group include a linear, branched or cyclic substituted or unsubstituted alkenyl group, and in addition to the alkenyl group, include a cycloalkenyl group and a bicycloalkenyl group.

Among the above alkenyl groups, those having 2 to 3 carbon atoms
0 substituted or unsubstituted alkenyl group (eg, vinyl group, allyl group, prenyl group, geranyl group, oleyl group)
Is preferred. Among the cycloalkenyl groups, a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopentene-1) −
Yl, 2-cyclohexen-1-yl group) is preferred.
Among the bicycloalkenyl groups, a substituted or unsubstituted bicycloalkenyl group is exemplified, and a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond is removed. Monovalent groups (for example, bicyclo [2,2,1] hept-
2-en-1-yl group and bicyclo [2,2,2] oct-2-en-4-yl group) are preferred.

Among the alkynyl groups, those having 2 to 3 carbon atoms
A substituted or unsubstituted alkynyl group of 0 is preferable, and for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group and the like are preferable.

Among the above aryl groups, those having 6 to 30 carbon atoms
Or a substituted or unsubstituted aryl group, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl.

Among the above heterocyclic groups, 5-membered or 6-membered
A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound having 1 to 3 carbon atoms is preferable, and a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms is preferable. Are more preferable, for example, a 2-furyl group, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like are particularly preferred.

Among the above alkoxy groups, those having 1 to 3 carbon atoms
A substituted or unsubstituted alkoxy group of 0 is preferable, for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-
Butoxy, n-octyloxy, 2-methoxyethoxy and the like are more preferred.

Among the above aryloxy groups, those having 6 carbon atoms
~ 30 substituted or unsubstituted aryloxy groups are preferred, for example, phenoxy group, 2-methylphenoxy group,
4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, and the like are more preferable.

Among the above silyloxy groups, those having 3 to 3 carbon atoms
20 silyloxy groups are preferred, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group,
And the like are more preferable.

Among the above heterocyclic oxy groups, those having 2 carbon atoms
A substituted or unsubstituted heterocyclic oxy group of up to 30 is preferable, and for example, a 1-phenyltetrazol-5-oxy group, a 2-tetrahydropyranyloxy group, and the like are more preferable.

Among the above acyloxy groups, a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms are preferable. , Formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy, and the like.

Among the carbamoyloxy groups, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms is preferred. For example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group Groups, N, N-di-n-octylaminocarbonyloxy groups, Nn-octylcarbamoyloxy groups, and the like are more preferred.

Among the above alkoxycarbonyloxy groups, a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms is preferable. For example, methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octyl A carbonyloxy group is more preferred.

Among the above aryloxycarbonyloxy groups, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms is preferable. For example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a pn- A hexadecyloxyphenoxycarbonyloxy group is more preferred.

Among the above amino groups, in addition to the amino group,
A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms,
Examples thereof include a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group.

Among the acylamino groups, a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, and the like are preferable. , Formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group,
A 3,4,5-tri-n-octyloxyphenylcarbonylamino group and the like are more preferred.

Among the above aminocarbonylamino groups,
A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms is preferable. For example, a carbamoylamino group, N,
More preferred are an N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group, and the like.

Among the above alkoxycarbonylamino groups, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms is preferable, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyl. An oxycarbonylamino group, an N-methyl-methoxycarbonylamino group, and the like are more preferred.

Among the above-mentioned aryloxycarbonylamino groups, a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms is preferable. For example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn- An octyloxyphenoxycarbonylamino group is more preferred.

Among the sulfamoylamino groups, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms is preferable. For example, a sulfamoylamino group, N,
An N-dimethylaminosulfonylamino group, an Nn-octylaminosulfonylamino group, and the like are more preferable.

Among the above-mentioned alkyl and arylsulfonylamino groups, a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms are preferable.
For example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-
A trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, and the like are more preferable.

Among the above alkylthio groups, those having 1 to 1 carbon atoms
30 substituted or unsubstituted alkylthio groups are preferable, and for example, a methylthio group, an ethylthio group, an n-hexadecylthio group, and the like are more preferable.

The arylthio group has 6 to 6 carbon atoms.
Preferred are 30 substituted or unsubstituted arylthio groups such as phenylthio, p-chlorophenylthio, m
-Methoxyphenylthio group, and the like are more preferred.

Among the above heterocyclic thio groups, those having 2 to 2 carbon atoms
30 substituted or unsubstituted heterocyclic thio groups are preferred, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group, and the like are more preferred.

Among the sulfamoyl groups, those having 0 carbon atoms
~ 30 substituted or unsubstituted sulfamoyl groups are preferred, for example, N-ethylsulfamoyl group, N- (3-
Dodecyloxypropyl) sulfamoyl group, N, N-
Dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N'-
Phenylcarbamoyl) sulfamoyl, and the like are more preferred.

Among the above-mentioned alkyl and arylsulfinyl groups, a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, and the like are preferable. An ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group and the like are more preferred.

Among the alkyl and arylsulfonyl groups, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms are preferable. Ethylsulfonyl group, phenylsulfonyl group, p-
A methylphenylsulfonyl group is more preferred.

Among the above acyl groups, a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms,
A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms is preferable, for example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxyphenylcarbonyl group,
And the like are more preferable.

Among the above-mentioned aryloxycarbonyl groups, a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms is preferable, and examples thereof include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group and a p-type. -T-butylphenoxycarbonyl group and the like are more preferable.

Among the above alkoxycarbonyl groups, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms is preferable, for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group and the like. Is preferred.

Among the carbamoyl groups, those having 1 to 1 carbon atoms
Preferred are 30 substituted or unsubstituted carbamoyl groups, for example, carbamoyl group, N-methylcarbamoyl group, N,
N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like are preferred.

Among the aryl and heterocyclic azo groups, a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms and a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms are preferable. Group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group, and the like are more preferable.

Among the imide groups, N-succinimide, N-phthalimide and the like are preferable. Among the phosphino groups, a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms is preferable, for example, a dimethylphosphino group,
Diphenylphosphino groups, methylphenoxyphosphino groups, and the like are more preferred. Among the phosphinyl groups, a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms is preferable, and for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like are preferable.

Among the phosphinyloxy groups, a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms is preferable. Examples thereof include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group. Is more preferred. Among the phosphinylamino groups, a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms is preferable, for example, a dimethoxyphosphinylamino group,
A dimethylaminophosphinylamino group is more preferred.

Among the above silyl groups, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms is preferable, and for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group and the like are more preferable.

Among the substituents on the heterocyclic group, those having a hydrogen atom may be obtained by removing the hydrogen atom and further substituting the substituent. As such a group, for example, an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, an arylsulfonylaminocarbonyl group are preferable, and among them, a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylamino A carbonyl group, an acetylaminosulfonyl group and a benzoylaminosulfonyl group are more preferred.

In the general formula (I), specific examples (A-1 to 25) of the monovalent heterocyclic group represented by A and B and bonded to the azo group by a carbon atom are shown below. The invention is not limited to these.

[0066]

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[0067]

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In the specific examples A-1 to A-25, R ²¹ to
R ⁵⁰ each independently represents a group selected from the above-mentioned substituents for the heterocyclic group. a, p, q, r, s
Represents an integer of 0 to 4. b and c represent an integer of 0 to 6. d, e, f, g, t, and u represent integers of 0 to 3.
h, i, j, k, l, and o represent integers of 0 to 2. a ~
When u represents 2 or more, two or more substituents represented by R ^{21 to} R ⁵⁰ may be the same or different from each other. For the adjacent ones of R ^{21 to} R ⁵⁰ ,
They may combine with each other to form a ring structure. The ring structure to be formed may be a hetero ring or a carbocyclic ring, and may be a saturated ring or an unsaturated ring. The number of ring members is preferably 5 or 6.

As the compound represented by the general formula (I) of the present invention, the heterocyclic group represented by A is preferably a group having the following structure among the preferred specific examples of the monovalent heterocyclic group. It is preferably a group selected from AI) to (A-VII).

[0070]

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Preferred examples of the heterocyclic group represented by A
In the examples (AI) to (A-VII), R⁶¹, R⁶²,
R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R⁷¹, R⁷², R
⁷³, R⁷⁴, R⁷⁵, R⁷⁶, R⁸¹, R⁸², R⁸³, R⁹¹,
R⁹², R⁹³, R⁹⁴, R⁹⁵, And R ⁹⁶Are each independently water
Represents an atom or a substituent. As the substituent, the aforementioned
Examples of the substituents of the ring group include:
Can be.

Among the above substituents, R ⁹¹ and R ⁹² are more preferably bonded to each other to form a 5- or 6-membered ring structure, and those having a benzene ring as the ring structure are further preferable. preferable. The benzene ring may have a substituent. Suitable examples of the substituent include the above-described examples of the substituent of the heterocyclic group, and among them, a sulfonic acid group (or a salt thereof) is preferable.

Among the above substituents, R ⁹³ is a nitro group, an alkylsulfonyl group, an arylsulfonyl group,
Alkylthio, arylthio, alkyl and aryl groups are preferred. Among the substituents, R ⁹⁵ and R ⁹⁶ are preferably a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, a cyano group, an alkyl group, and an aryl group. Among the above substituents, R ⁹⁴ is preferably a hydrogen atom, an alkyl group, or an aryl group.

Among the above substituents, R⁶¹, R⁶², R⁶³,
R⁶⁴, R⁶⁵, R⁶⁶, R⁶⁷, R⁶⁸, R ⁷¹, R⁷², R⁷³, R
⁷⁴, R⁷⁵, R⁷⁶Are each independently a hydrogen atom, chlorine
Atom, sulfonic acid group, carboxylic acid group, alkyl group, azo
Groups, alkylsulfonyl groups and nitro groups are preferred. Said
Among the substituents, R⁸¹Represents an alkyl group, an aryl
Group, cyano group, carboxylic acid group, alkoxycarbonyl
Group, aryloxycarbonyl group, and acyl group are preferred.
No.

Among the above substituents, R ⁸² is preferably an alkyl group, an aryl group, a cyano group, a carboxylic acid group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Among the above substituents, R ⁸³ is a hydrogen atom,
Alkyl, aryl and heterocyclic groups are preferred.

In the compound of the present invention represented by the above general formula (I), a heterocyclic group represented by B is preferably a group having the following structure among the preferred specific examples of the above monovalent heterocyclic group. It is preferably a group selected from (BI) to (B-VII).

[0077]

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In the preferred specific examples of the heterocyclic group represented by B, (BI) to (B-VII), R ^{101 to} R ¹¹⁶
Represents a hydrogen atom or a substituent each independently. Also, Q
¹¹ , Q ¹² and Q ¹³ together with N atoms at both ends represent an atomic group necessary to complete a 5- or 6-membered heterocyclic ring.
Preferred specific examples of the heterocyclic group represented by B (B-
Among (I) to (B-VII), the following (B-IA), (B-VII)
-IIA), (B-IIIA), (B-IVA), (BV
A), (B-VIA), (B-VIB), and (B-VII)
Groups having the structure represented by A) are more preferred.

[0079]

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[0080] In an embodiment of the more preferred groups as the heterocyclic group represented by ^{B, R 10 1 ~R 116,} R 121 ~
R ¹²⁴ represents a hydrogen atom or a substituent. Examples of the substituent include those described above as the substituents that can be substituted on the heterocycle represented by A and B.
R ¹⁰¹ and R ¹⁰² are each independently preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,
An unsubstituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms are more preferable. Among them, R ¹⁰¹ is particularly preferably an unsubstituted alkyl group having 1 to 30 carbon atoms, and R ¹⁰² is particularly preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. As ^R103 , a hydroxyl group and an amino group are preferable.

As R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁷ , those similar to the aforementioned R ¹⁰² are preferable. The R ^{10 6,} hydroxyl groups, is preferably a substituted or unsubstituted amino group, when an amino group, an amino group substituted with an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms Substituted amino groups are more preferred.

As R ¹⁰⁸ and R ¹¹¹ , a hydroxyl group,
A substituted or unsubstituted amino group is preferred. As R ¹⁰⁹ , a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are preferable. Among them, an unsubstituted alkyl group having 1 to 22 carbon atoms is more preferable. As R ¹¹⁰ , a cyano group, a carboxyl group, a substituted or unsubstituted aminocarbonyl group is preferable, and among them, a cyano group is particularly preferable.

As R ¹¹² , a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are preferable, and among them, an unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferable. Z ¹ and Z ² each independently represent -C (R ¹²⁶ ) = or -N =. R ¹²⁶ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among them, ^one of Z ¹ and Z ² is preferably -C (R ¹²⁶ ) = and the other is -N =, and Z ² is preferably -C (R ¹²⁶ ) =.
(R ¹²⁶ ) = and Z ¹ is -N = are particularly preferred. As R ¹²⁶ , a substituted aryl group having 6 to 30 carbon atoms and an unsubstituted alkyl group having 1 to 8 carbon atoms are preferable.

R ¹¹³ is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among them, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,
A substituted or unsubstituted aryl group having 6 to 30 carbon atoms is preferable, and an unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferable.
R ¹¹⁴ is preferably a substituted or unsubstituted amino group. Among them, an amino group substituted with an unsubstituted alkyl group having 1 to 30 carbon atoms, and an amino group substituted with a substituted or unsubstituted aryl group having 6 to 30 carbon atoms are more preferable.
An amino group substituted with an unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferred.

Each of R ¹²¹ and R ¹²² is preferably independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among them, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms is more preferable, and an unsubstituted alkyl group having 1 to 8 carbon atoms is particularly preferable. In addition, R ¹²¹ and R
Preferably, ¹²² are the same as each other.

Each of R ¹²³ and R ¹²⁴ is preferably independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among them, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms are preferable, and an unsubstituted alkyl group having 1 to 8 carbon atoms and 6 to 3 carbon atoms.
A substituted aryl group of 0 is particularly preferred.

As R ¹¹⁵ and R ¹¹⁶ each independently, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a cyano group, and a substituted or unsubstituted alkoxycarbonyl group are preferred. Among them, R ¹¹⁵ is preferably a cyano group or a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, and particularly preferably a cyano group. R ¹¹⁶
Is preferably a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, and particularly preferably an unsubstituted alkyl group having 1 to 30 carbon atoms. Z ³ and Z ⁴ are each independently-
C (R ¹²⁷ ) = or -N =. R ¹²⁷ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Among them, one of Z ³ and Z ⁴ is -C (R
¹²⁷ ) = and the other is preferably -N =, Z ³
Is particularly preferably -N = and Z ⁴ is -C (R ¹²⁷ ) =. R ¹²⁷ is preferably a substituted aryl group having 6 to 30 carbon atoms or an unsubstituted alkyl group having 1 to 8 carbon atoms.

In the general formula (I), m and n are
Each independently represents 0 or 1. Among them, m is 0 or 1
And n is preferably 1, m is 0, and n
Is more preferably 1.

In the general formula (I), M represents a hydrogen atom or a monovalent cation. Examples of the monovalent cation include an alkali metal ion (eg, sodium ion, potassium ion, lithium ion) and an alkaline earth metal ion (eg, 1/2 calcium ion, 1/2
Magnesium ions), other metal ions (for example,
Preferred examples include a ア ル ミ ニ ウ ム aluminum ion), a transition metal ion (eg, 亜 鉛 zinc ion), and an organic cation (eg, tetraalkylammonium ion).
Among them, M is preferably a sodium ion, a potassium ion, or a hydrogen atom.

In the compound represented by the general formula (I) of the present invention, A and B are preferably different heterocyclic groups, and one or more sulfonic acid groups (or Is preferred.

The compound represented by the formula (I) of the present invention is a water-soluble dye, and has a black color because it has two broad absorption bands in the visible region. Among the two absorption bands, one having an absorption band peak at 430 to 480 nm and the other absorption band peak at 550 to 630 nm is preferable, and one of the two absorption bands is preferred. More preferably, the peak exists at 430 to 460 nm and the other absorption band peak exists at 570 to 600 nm, and the absorption band peak formed by the heterocyclic group represented by A and the azo group exists at 550 to 630 nm. And an azo group (-N = N-) represented by a heterocyclic group represented by B or B and having an absorption band peak at 430 to 480 nm. Assignment of the two absorption bands can be confirmed by synthesizing the corresponding monoazo dye.

The compound represented by formula (I) of the present invention may form a so-called chelate dye by coordinating with a metal ion depending on the structure. Various known metal ions are used for the chelate. Among them, copper ion, nickel ion, iron ion, cobalt ion, zinc ion, chromium ion and the like are preferably used. However, the chromium ions are toxic. For this reason, it is not preferable to use chromium ions for applications where humans come into direct contact with each other, such as ink-jet inks. On the other hand, in applications where humans do not come into direct contact,
Chromium ions can be used. Chromium chelate dyes may improve light fastness, and are preferably used when high fastness is required. Accordingly, from the viewpoint of compatibility between the required performance of the dye such as toxicity and fastness, the compound of the present invention is more preferably a copper chelate.

Specific examples (II-1 and 2) of preferred structures when the compound of the present invention is used as a chelating dye are shown below, but the present invention is not limited thereto.

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In the specific examples (II-1) and the general formula (II-2) of the preferred structure, M ¹ and M ² represent metal ions. Q ¹ and Q ² are an atomic group forming a heterocyclic group represented by A in the general formula (I). L represents a ligand coordinated to the metal ion. z represents an integer of 0 or more, and is determined to be a unique number by a metal ion. m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. B is
Represents a monovalent heterocyclic group bonded to an azo group by a carbon atom.

Specific examples (exemplary compounds 1 to 32) of the compound represented by the above general formula (I) of the present invention are shown below.
The present invention is not limited to these.

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[0098]

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[0101]

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[0102]

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<Synthesis Method of Compound Represented by General Formula (I)> Here, a synthesis method of the compound represented by the general formula (I) of the present invention will be described. The compound of the present invention can be synthesized by a method represented by the following route A or route B.

[0104]

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[0105]

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In the route A, a diazonium salt of a β-naphthylamine derivative is synthesized, a coupler corresponding to the coupler component B is reacted, and a monoazo intermediate C (having the coupler component B) is synthesized. With a corresponding diazonium salt. On the other hand, the route B
A diazonium salt corresponding to the diazo component A is reacted with a β-naphthylamine derivative to synthesize a monoazo intermediate E (having the diazo component A), diazotize the monoazo intermediate and give a coupler B as a coupler. And the compound of the present invention is synthesized.

Regarding the azo coupling reaction,
It is described in "The Chemistry of Synthetic Dyes" (Konzo Konishi and Nobuhiko Kuroki, Maki Shoten, Tokyo, 1963).

(Dye, Coloring Composition, Ink, and Ink for Ink) Here, the dye of the present invention, the coloring composition containing the dye, the ink, and the ink for ink jet will be described. Since the compound represented by the general formula (I) of the present invention is a direct dye due to its physical properties, it can dye a material made of cellulose. Further, since it is possible to dye other materials having a carbonamide bond, it can be widely used for dyeing leather, woven fabric, and paper. On the other hand, typical uses of the coloring matter of the present invention include coloring compositions, inks, and inkjet inks dissolved in a liquid medium.

The dye of the present invention is characterized by containing the compound represented by formula (I). The coloring composition containing the coloring matter of the present invention is prepared by dissolving the compound represented by the general formula (I) in water or water further containing other water-soluble substances.

In preparing the coloring composition, other water-soluble substances are contained within a range that does not impair the effects of the compound of the present invention. Other water-soluble substances include organic solvents (water-soluble), additives, bactericides, fungicides, and the like.

Examples of the organic solvent include alcohols, ethers, carbonamides, ureas, esters, sulfones, sulfonamides, esters, and nitriles. Among them, for example, methanol, ethanol , Propanol, ethylene glycol, its monomethyl ether, 1,2-propylene glycol and the like are preferred. In addition, it is also preferable to use an organic solvent described in JP-A-11-349835. These organic solvents may be used alone or in combination of two or more.

As the additives, for example, viscosity adjusters, surface tension adjusters, pH adjusters, defoamers, anti-drying agents, penetration enhancers, ultraviolet absorbers, antioxidants and the like are preferably exemplified. It is preferable that the viscosity and the surface tension of the coloring composition containing the dye of the present invention are adjusted to optimal ranges by adjusting the ion concentration using the viscosity adjusting agent and the surface tension adjusting agent. In addition, as the other substance soluble in water, the above-mentioned bactericide and fungicide can be used.

As the surface tension adjusting agent, nonionic,
Preference is given to cationic or anionic surfactants.

Examples of the pH adjusting agent include hydroxides of alkali metals such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, and the like.
Examples include inorganic bases such as potassium acetate, sodium silicate, and disodium phosphate; and organic bases such as N-methyldiethanolamine and triethanolamine.

The pH of the coloring composition is preferably from 6 to 10 from the viewpoint of improving storage stability.
7 to 10 are more preferred. Further, the surface tension of the coloring composition is preferably from 25 to 70 mN / m, and is preferably from 25 to 60 mN / m.
mN / m is more preferred. Further, the viscosity of the coloring composition is preferably 30 mPa · s or less, and 20 mPa · s or less.
s or less is more preferable.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used if necessary.

The above-mentioned anti-drying agent can be used to dry the ink when the coloring composition containing the coloring matter of the present invention is used in the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording system. It is suitably used for the purpose of preventing clogging due to the above.

As the drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol,
Thiodiglycol, dithiodiglycol, 2-methyl-
Polyhydric alcohols represented by 1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl)
Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine And the like, a sulfur-containing compound such as sulfolane, dimethyl sulfoxide and 3-sulfolene, a polyfunctional compound such as diacetone alcohol and diethanolamine, and a urea derivative. Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferable. These may be used alone or may be used alone.
More than one species may be used in combination. These drying inhibitors are preferably contained in the coloring composition in an amount of 10 to 50% by mass.

The penetration enhancer is suitably used for the purpose of allowing the coloring composition to penetrate the paper better. Examples of the penetration enhancer include ethanol, isopropanol,
Examples thereof include alcohols such as butanol, di (tri) ethylene glycol monobutyl ether, and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and a nonionic surfactant. The penetration enhancer is contained within a range that does not cause bleeding of printing, paper dropout (print-through), and the like, and generally exerts a sufficient effect when contained in the coloring composition in an amount of about 5 to 30% by mass.

The above-mentioned ultraviolet absorber is used for the purpose of improving the storability of an image, for example, as described in JP-A-58-1856.
Nos. 77, 61-90537 and JP-A-2-
No. 782, No. 5-1970075, No. 9-34
Benzotriazole compounds described in JP-A-557 / 057, JP-A-46-2784, JP-A-5-1944
No. 83, U.S. Pat. No. 3,214,463, benzophenone-based compounds described in JP-B-48-30492, JP-B-56-21141, and JP-A-10-881.
No. 06, etc., cinnamic acid-based compounds,
298503, 8-53427 and 8-
Nos. 239368, 10-182621, and JP-A-8-501291, and the like. 2423
Compounds described in No. 9 and compounds that absorb and emit fluorescence, such as stilbene-based and benzoxazole-based compounds, that emit fluorescence, so-called fluorescent whitening agents, and the like.

The antioxidant is used for the purpose of improving the storability of an image. For example, various organic and metal complex-based anti-fading agents can be used. Examples of the organic fading inhibitor include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans,
Alkoxyanilines, heterocycles, and the like. Examples of the metal complex-based anti-fading agent include a nickel complex, a zinc complex, and the like. Nos. 17643, VII, I to J; 15162; No. 18716, page 650, left column, ibid. No. 36544, page 527; 3071
No. 05, page 872; Compounds described in the patent cited in US Pat. No. 15,162, and the compounds represented by the general formulas and examples of typical compounds described on pages 127 to 137 of JP-A-62-215272 can be used. .

Examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. Can be These are present in the colored composition
It is preferred to use 1.00% by mass.

The coloring composition containing the coloring matter of the present invention includes:
Other pigments having various hues may be mixed to finely adjust the black tint. In that case, a dye of yellow, magenta, cyan or other colors can be used in addition to the compound of the present invention.

In the coloring composition containing the coloring matter of the present invention, the compound represented by the general formula (I) is preferably 0.5 to 2
It is preferably contained in the range of 0% by mass, and 3 to 10%.
More preferably, it is contained by mass%.

The dye of the present invention can be used in various fields, but is preferably used for an ink, and is suitable for an aqueous ink for writing, an aqueous printing ink, an information recording ink, and the like. It is particularly preferable to use it as an inkjet ink. Therefore, the ink of the present invention and the ink for ink jet are characterized by containing the coloring matter of the present invention, and the ink for ink jet of the present invention is suitably used in the ink jet recording method of the present invention described later.

(Ink Jet Recording Method) Next, the ink jet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using an inkjet ink containing the dye. In the inkjet recording method of the present invention, recording is performed on an image receiving material using an inkjet ink containing the dye, but there is no particular limitation on an ink nozzle or the like used at that time, and the You can choose.

The image receiving material is not particularly limited.
Known recording materials, for example, plain paper, resin-coated paper, inkjet-only paper, film, electrophotographic paper, fabric,
Glass, metal, porcelain and the like can be mentioned. Among the recording materials, inkjet-dedicated paper is preferable. For example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, and JP-A-9-323475. JP-A-62-238
No. 783, Japanese Unexamined Patent Publication No. 10-153899,
Nos. 0-217473, 10-235995, 10-337947, and 10-21759.
No. 7, JP-A-10-337947, and the like are more preferable.

In the ink jet recording method of the present invention, the following recording papers and recording films are particularly preferable among the image receiving materials.

The recording paper and the recording film are formed by laminating a support and an image receiving layer, and if necessary, laminating other layers such as a back coat layer. Each of the layers including the image receiving layer may be a single layer,
It may have more than one layer.

As the support, LBKP, NBKP
Chemical pulp, GP, PGW, RMP, TMP, CT
MP, CMP, mechanical pulp such as CGP, waste paper pulp such as DIP, etc., if necessary, conventional known pigment, binder, sizing agent, fixing agent, cationic agent, paper strength enhancer, etc. Those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used. In addition, synthetic paper, plastic film sheets, and the like may be used.

The thickness of the support is preferably from 10 to 250
It is about μm, and the basis weight is desirably 10 to 250 g / m ² .

The support may be provided with the image receiving layer, the back coat layer, or a size press with starch, polyvinyl alcohol or the like. An image receiving layer and the back coat layer may be provided. The support may be subjected to a flattening process using a calender such as a machine calender, a TG calender, and a soft calender.

Among the above-mentioned supports, paper and plastic films, both surfaces of which are laminated with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof), are preferably used. It is more preferable to add a white pigment (for example, titanium oxide, zinc oxide, etc.) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide, etc.) to the polyolefin.

In the image receiving layer, a pigment, an aqueous binder,
It contains a mordant, a waterproofing agent, a lightfastness improving agent, a surfactant, and other additives.

The pigment is preferably a white pigment.
Examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite,
Inorganic white pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, zinc carbonate, styrene pigment, acrylic pigment, urea resin, melamine resin,
And the like. Among these white pigments, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is more preferable. As the synthetic amorphous silica, any of silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder include water-soluble binders such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. These aqueous binders may be used alone or may be used alone.
More than one species may be used in combination. Among these, polyvinyl alcohol, silanol modified polyvinyl alcohol,
It is preferable in terms of adhesion to the pigment and peel resistance of the image receiving layer.

It is preferable that the mordant is immobilized. For this purpose, a polymer mordant is preferably used. As the polymer mordant, JP-A-Showa 4
8-28325, 54-74430, 54-1
No. 24726, No. 55-22766, No. 55-142
No. 339, No. 60-23850, No. 60-23851
Nos. 60-23852, 60-23853, 60-57836, 60-60643, 60-
No. 118834, No. 60-122940, No. 60-1
No. 22941, No. 60-122942, No. 60-23
5134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, and 314.
No. 8061, No. 3309690, No. 4115124
Nos. 4,124,386, 4,193,800, 42
No. 73853, No. 4282305, No. 4450224
No. is described in each specification. Polymer mordants described on pages 212 to 215 of JP-A-1-161236 are particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant, and a cationic resin is preferred. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone,
Examples thereof include a dimethyldiallylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Of these, polyamide polyamine epichlorohydrin is particularly preferred. The content of the cationic resin is 1 to 15% by mass based on the total solid content of the image receiving layer.
Is preferably, and more preferably 3 to 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzophenone and benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferable.

The surfactant functions as a coating aid, a release improver, a slipperiness improver or an antistatic agent. Examples of the surfactant include JP-A-62-17346.
No. 3, No. 62-183457. An organic fluoro compound may be used instead of the surfactant. The organic fluoro compound,
Preferably, it is hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil) and a solid fluorine compound resin (for example, ethylene tetrafluoride resin). The organic fluoro compound is described in
No. 9053 (columns 8 to 17), JP-A-61-20994
And JP-A-62-135826.

Examples of the other additives include a pigment dispersant, a thickener, an antifoaming agent, a dye, a fluorescent brightener, a preservative, a pH adjuster, a matting agent, and a hardening agent.

The back coat layer contains a white pigment, an aqueous binder, and other components.

Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc,
Calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo boehmite, hydroxylated White inorganic pigments such as aluminum, alumina, lithopone, zeolite, hydrohaloysite, magnesium carbonate, magnesium hydroxide, etc .; organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, melamine resin, etc. Can be

As the aqueous binder, styrene /
Water-soluble polymers such as maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, and styrene Water-dispersible polymers such as butadiene latex and acrylic emulsion are exemplified.

Examples of the other components include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

Incidentally, a polymer latex may be added to the constituent layers (including the back coat layer) in the recording paper and recording film. The polymer latex,
It is used for the purpose of improving film properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. About the polymer latex, JP-A-62-245258,
It is described in JP-A-62-1316648 and JP-A-61-10066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing the mordant, cracking and curling of the layer can be prevented. When a polymer latex having a high glass transition temperature is added to the back coat layer, curling can be prevented.

The ink-jet recording method of the present invention is not particularly limited, and is a known method, for example, a charge control method for discharging ink by using electrostatic attraction, a drop-on-demand using vibration pressure of a piezo element. A method (pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate ink to eject ink using radiation pressure, and a thermal method that heats ink to form bubbles and uses the generated pressure Any of an ink jet (bubble jet (R)) method or the like may be used. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue and different densities, and a method of colorless and transparent. A method using ink is included.

[0148]

The present invention will be described below with reference to examples.
The present invention is not limited at all by the following Examples. (Example 1) <Synthesis of compound 23> First, compound 23 (dye 23) mentioned as an exemplary compound was synthesized through the following steps.

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-Step 1-4.0 g (17 mmol) of gamma acid was dissolved in 50 ml of water,
1.38 g of sodium hydroxide and sodium nitrite
(21 mmol) was added. 6.97 ml of concentrated hydrochloric acid (84
mmol) and 50 ml of water were stirred at 5 ° C., and the above solution was added dropwise. The mixture was stirred for 4 hours to prepare a diazo solution of γ-acid.

-Step 2-Coupler B was dissolved in a mixture of 50 ml of water and 50 ml of methanol. Then, 11.5 g of potassium acetate (17
0 mmol), and the diazo solution of γ-acid prepared in the above step 1 was added dropwise while stirring at 5 ° C. The mixture was stirred for 30 minutes, and the precipitated crystals were collected by filtration and dried to obtain 5.9 g of monoazo intermediate C (yield 70%).

Step 3 0.1 g (0.66 mmol) of the diazo component A was added to 50 parts of water.
A solution of 0.055 g (0.79 mmol) of sodium nitrite dissolved in 10 ml of water was added dropwise to the solution while stirring. The mixture was stirred for 30 minutes to prepare a diazo liquid containing diazonium salt D. -Step 4-0.3 g (0.59 mmol) of monoazo intermediate C, 0.32 g (5.62 mmol) of potassium hydroxide, 50 m of water
to the place where the solution was stirred at 5 ° C.
Was added dropwise. After stirring for 2 hours, the mixture was allowed to stand at room temperature for 12 hours, and acetone was added to the reaction solution to precipitate a solid, which was collected by filtration. The obtained solid was purified using a Sephadex column to obtain Compound 23. When the mass spectrum was measured and the structure of the obtained compound 23 was identified, the parent peak (M-1) was found to be 65%.
8 (negative). In addition, the obtained compound 23
PKa (acid dissociation index) at 25 ° C. in a solution of tetrahydrofuran: water = 60: 40 (volume ratio)
Was measured, the first dissociation was 7.9 and the second dissociation was 12.6.

<Synthesis of Compound 24> Copper acetate (Cu (OC
Using OCH ₃ ) ₂ ), compound 23 (dye 23) was subjected to copper chelation to synthesize compound 24 (dye 24).
FIG. 1 shows the result of measuring the reflection spectrum of a recorded image using an inkjet ink containing Compound 24 (Dye 24).

<Synthesis of Compound 30> The compound 30 (dye 30) mentioned as an example compound was synthesized through the following steps.

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-Step 1- 7.98 g (33.3 mmol) of gamma acid, 67 ml of water, 1.47 g (36.8 mmol) of sodium hydroxide, 2.42 g (36.8 mmol) of sodium nitrite were added at room temperature for 20 minutes. Stir for a minute to dissolve. 14.2 ml of concentrated hydrochloric acid (1
6.5 mmol) and 20 ml of water were stirred under ice-cooling, and the above solution was added dropwise over 15 minutes. Meanwhile, the temperature of the reaction solution was 2 ° C to 4 ° C. After stirring for 4 hours, 0.2 g (2.06 mmol) of sulfamic acid was added.
l) The mixture was stirred at 5 ° C. for 30 minutes to prepare a diazonium salt of gamma acid (diazonium salt 1).

-Step 2-8.5 g (31.3 mmol) of coupler 1, 24.5 g (250 mmol) of sodium acetate, and 150 g of water
While stirring under ice-cooling, a diazo solution containing the diazonium salt 1 prepared in Step 1 was added dropwise over a total amount of 15 minutes. The reaction was carried out at a reaction temperature of 5 ° C. for 1 hour and at 10 ° C. for 1 hour. When allowed to stand overnight, crystals had precipitated. Acetonitrile 700 ml, methanol 4
0 ml was added and the mixture was stirred, and the crystals were collected by filtration. After drying, 10.67 g of azo compound 1 was obtained (63.0% yield).

-Step 3-0.72 g (5.0 mmol) of 8-aminoquinoline,
2.2 ml (25 mmol) of concentrated hydrochloric acid was added while stirring 20 ml of water under ice-cooling. Further, 0.38 g (5.5 mmol) of sodium nitrite was added to 3.8 m of water.
1 was added dropwise for 5 minutes. After reacting for 2 hours under ice cooling, 0.049 g of sulfamic acid (5.0 mm
ol) and reacted for 30 minutes to obtain diazonium salt 2
Was prepared.

Step 4 Azo compound 1 3.0 g (5.5 mmol), water 210
The diazonium salt 2 was added dropwise over 15 minutes while stirring the mixture under ice-cooling with 70 ml of dimethylacetamide and 4.6 g (56 mmol) of sodium acetate. 2
After reacting for hours, the mixture was allowed to stand at room temperature overnight, whereupon crystals were precipitated. 1000 ml of acetonitrile in the reaction solution
After stirring, the crystals were collected by filtration. The crude product was purified using a Sephadex column to obtain 1.94 g of Compound 30 (Dye 30) (yield: 52%). Compound 30 obtained
(Dye 30) in deuterated dimethyl sulfoxide
FIG. 2 shows the measurement results of the ¹ H-NMR spectrum (300 MHz). FIG. 3 shows the measurement results of the absorption spectrum of the obtained compound 30 in dimethylformamide.

<Synthesis of Compound 29> Copper acetate (Cu (OC
Compound 30 (dye 30) was subjected to copper chelation using OCH ₃ ) ₂ ) to synthesize compound 29 (dye 29).
FIG. 4 shows the measurement results of the absorption spectrum of the obtained compound 29 (dye 29) in water.

<Synthesis of Compound 31> The compound 31 (dye 31) mentioned as an example compound was synthesized through the following steps.

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-Step 1-Compound 2 1.0 g (2.9 mmol), phosphoric acid 10 g
While stirring under ice-cooling, 0.21 g (3 mmol) of sodium nitrite was added over 5 minutes. Thereafter, the reaction was carried out at 5 ° C. for 2 hours to prepare diazonium salt 3.

Step 2 0.3 g (0.577 mmol) of the azo compound 1, 20 ml of dimethylacetamide, 10 ml of water, and 0.38 g (4.63 mmol) of sodium acetate were stirred under ice-cooling. The diazo liquid of diazonium salt 3 prepared in the above was dropped over 15 minutes. After reacting for 2 hours under ice-cooling, the mixture was allowed to stand at room temperature overnight, whereupon crystals were precipitated. Acetonitrile (1000 ml) was added to the reaction solution, the mixture was stirred, and the crystals were collected by filtration. The crude product was purified using a Sephadex column to obtain 0 and 28 g of Compound 31 (Dye 31) (yield: 56%). Compound 31 obtained (Dye 31)
FIG. 5 shows the results of measurement of the absorption spectrum in water for. Further, measurement results of the compound 31 ¹ H-NMR spectrum in heavy dimethylsulfoxide in (dye 31) (300 MHz) shown in FIG.

<Preparation of Comparative Ink Set 101> After adding deionized water to the following components to make 1 liter,
The mixture was stirred for 1 hour while heating at 40 ° C. Then KOH1
The pH was adjusted to 9 at 0 mol / l, and the average pore size was 0.25.
The solution was filtered under reduced pressure through a micro filter of μm to prepare a black ink for comparison.

—Comparative Black Ink— Black Dye T3 20.0 g Black Dye T5 20.0 g Black Dye T6 20.0 g Black Dye T7 20.0 g Diethylene glycol 20 g Glycerin 120 g Diethylene glycol monobutyl ether 230 g -Pyrrolidone 80 g Triethanolamine 17.9 g Benzotriazole 0.06 g Surfynol TG 8.5 g PROXEL XL2 1.8 g

Further, by changing the coloring matter and additives in the comparative black ink as shown in Table 1 below, light magenta ink, magenta ink,
Light cyan ink, cyan ink, and yellow ink were prepared, and a comparative ink set 101 shown in Table 1 was produced.

[0168]

[Table 1]

[0169]

Embedded image

[0170]

Embedded image

<Ink Sets 102 to 124 and 126
Preparation of -128> In the comparative ink set 101, the pigment used in the black ink was changed to the compound of the present invention, and the ink sets 102 to 124 and 126 to
128 were produced. The amount of the compound of the present invention used in each of the ink sets 102 to 124 and 126 to 128 is shown in parentheses in Table 2 below (g).

<Preparation of Comparative Ink Set 125> A comparative ink set 125 was prepared by changing the dye used in the black ink in the comparative ink set 101 to the following comparative dye a. Comparative dye a is Pol
yhedron 11 (13), 1597-1600
(1992).

[0173]

[Table 2]

[0174]

Embedded image

<Evaluation of Recorded Image> Ink set 10
1 to 128 for the inkjet printer PM670C
The image was recorded on an inkjet paper photo glossy paper EX (manufactured by Fuji Photo Film Co., Ltd.), and the following evaluation was performed. The evaluation results are shown in Table 3 below.

-Evaluation of color tone- To evaluate the color tone, the black part of the image recorded on the photo glossy paper was evaluated by visual observation. When there was no sample, the evaluation was made in two steps.

-Evaluation of Paper Dependency- As the evaluation of the paper dependence of the image, the color tone of the image formed on the photo glossy paper and the image formed on the high quality paper for PPC was evaluated by visual observation. The case where the difference is small is indicated by ○ (good), and the case where the difference between both images is large is indicated by
The evaluation was made in two stages.

-Evaluation of Water Resistance- For the evaluation of water resistance, the obtained image was air-dried and then dried.
After immersion in deionized water for 2 seconds, the bleeding of the image was visually evaluated. When no bleeding occurred, it was evaluated as O (good), and when bleeding occurred, it was evaluated as x (poor). .

Regarding the image storability, a print sample was prepared and evaluated for light resistance, dark heat storability, and ozone resistance in the following manner. -Light fastness evaluation-As the light fastness evaluation, the image density Ci immediately after printing was calculated using X-
After irradiating the image with xenon light (85,000 lux) for 7 days using a weather meter manufactured by Atlas, the image density Cf was measured again.
The residual dye ratio Ci / Cf * 100 was determined and evaluated. Regarding the dye remaining rate, the reflection density was evaluated at three points of 1, 1.5, and 2; C was less than 70% at all concentrations.

-Evaluation of Dark Storage Stability- The evaluation of the storage stability under dark conditions was made by measuring the image density of the sample before and after storing the sample for 7 days under the conditions of 80-15% RH.
The measurement was performed using X-rite 310, and the residual dye ratio was determined and evaluated. Regarding the dye remaining ratio, the reflection densities were 1, 1.
Evaluation was made at three points of 5, 2; A indicates that the residual ratio of the dye was 90% or more at any concentration, B indicates that the percentage of the dye was less than 90%, and C indicates that the percentage was less than 90% at all concentrations. did.

-Ozone resistance evaluation-The ozone resistance was evaluated as follows.
The image density of the sample before and after storage at 0.1 ppm, room temperature, and a dark place for 24 hours was measured using an X-rite 310.
And the dye residual ratio was determined and evaluated. The dye residual ratio was evaluated at three points where the reflection density was 1, 1.5, and 2. When the dye residual ratio was 70% or more at any of the densities, A2
The case where the point was less than 70% was B, and the case where the point was less than 70% at all concentrations was C.

[0182]

[Table 3]

From the evaluation results shown in Table 3 above, it was found that Sample 101 obtained by mixing and using known black dyes T3, T5, T6 and T7.
It was confirmed that the sample 125 was inferior in ozone resistance and light resistance, and that the sample 125 using the known dye a did not exhibit black color. On the other hand, in the samples 102 to 124 and 126 to 128 using the compound of the present invention, as a result of the printing test, it was confirmed that each of the samples exhibited high density, neutral black color, and was excellent in various fastnesses. That is,
The inks of the examples containing the compound of the present invention have excellent printing performance, good color tone, low paper dependence, excellent water resistance without bleeding, light fastness,
It became clear that the image storage properties such as dark heat storage property and ozone resistance were excellent.

(Example 2) The same ink produced in Example 1 was applied to an ink jet printer BJ-F850 (CA
NON Co., Ltd.), the recorded image was recorded on an inkjet paper photo glossy paper EX (manufactured by Fuji Photo Film Co., Ltd.), and the same evaluation as in Example 1 was performed. Similar results were obtained.

[0185]

According to the present invention, first, it exhibits a high density, neutral, colorless black, satisfies various performances required for pigments, inks and ink jet inks, is inexpensive, and can be synthesized. It can provide a novel compound that is easy to use. Secondly, it has excellent printing performance, good color tone, low paper dependence, excellent water resistance without bleeding, light resistance, and dark heat. It is possible to exhibit high density black, which is excellent in preservability and image preservability such as ozone resistance,
It is possible to provide a novel dye containing the compound, and an ink and an ink-jet ink containing the dye. Third, by using the ink-jet ink, an excellent image performance is obtained. An ink jet recording method that gives a black image can be provided.

[Brief description of the drawings]

FIG. 1 is a measurement result of a reflection spectrum of an image recorded by an inkjet ink containing Compound 24.

FIG. 2 shows a ¹ H-NMR spectrum of compound 30 (dye 30) in deuterated dimethyl sulfoxide (300
MHz).

FIG. 3 is a measurement result of an absorption spectrum of the obtained Compound 30 in dimethylformamide.

FIG. 4 is a measurement result of an absorption spectrum in water of Compound 29 (Dye 29).

FIG. 5 shows a measurement result of an absorption spectrum in water of compound 31 (dye 31).

FIG. 6 shows a ¹ H-NMR spectrum of compound 31 (dye 31) in deuterated dimethyl sulfoxide (300
MHz).

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] February 28, 2002 (2002.2.2)
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

Embedded image In the general formula (I), A and B each independently represent
Represents a monovalent heterocyclic group bonded to an azo group by a carbon atom.
m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are
It is not at the same time 1H-pyrazol-3-yl.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

<2> A dye represented by the following general formula (I):

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

In the general formula (I), A and B are
Each independently represents a monovalent heterocyclic group bonded to the azo group by a carbon atom. However, A and B are not simultaneously 1H-pyrazol-3-yl. Examples of the monovalent heterocyclic group represented by A include an oxygen atom, a sulfur atom, and a nitrogen atom.
Having in the ring at least one heteroatom selected from oxygen atom, a hetero ring is preferable 5- or 6-membered. Among them, from the viewpoint of the stability of the diazonium salt, an aromatic hetero ring is more preferable, and a hetero ring having 2 to 30 carbon atoms is more preferable. The monovalent heterocyclic group represented by A may be further condensed with another ring, and among the condensed ones, a condensed 5- or 6-membered ring is preferable.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

On the other hand, as the monovalent heterocyclic group represented by B, a monovalent heterocyclic group having at least one heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom in the ring can
Membered or 6-membered heterocycles are preferred. Among them, an aromatic hetero ring is more preferable, and the hetero ring has 2 to 30 carbon atoms.
Are more preferred. The monovalent heterocyclic group represented by B may be further condensed with another ring, and among the condensed ones, a condensed 5- or 6-membered ring is preferable.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

The dye of the present invention is represented by the above general formula (I).
It is characterized by being performed. The coloring composition containing the coloring matter of the present invention is prepared by dissolving the compound represented by the general formula (I) in water or water further containing other water-soluble substances.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 401/12 C07D 405/12 405/12 409/12 409/12 417/12 417/12 487/04 136 487/04 136 139 139 142 142 C09B 31/28 C09B 31/28 45/02 45/02 C09D 11/00 C09D 11/00 B41J 3/04 101Y Photo Film Co., Ltd. (72) Inventor Tadashi Omatsu 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Co., Ltd. F-term (reference) 4C063 AA01 BB09 CC22 CC61 CC67 CC82 CC92 DD11 DD22 DD25 EE10 4J039 BC41 BC51 BC73 BC79 BE01 BE02 BE12 CA06 EA19 GA24

Claims (6)

[Claims] 1. A compound represented by the following general formula (I). Embedded image In the general formula (I), A and B each independently represent
Represents a monovalent heterocyclic group bonded to an azo group by a carbon atom.
m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are
It is not at the same time 1H-pyrazol-3-yl. 2. A dye comprising a compound represented by the following general formula (I). Embedded image In the general formula (I), A and B each independently represent
Represents a monovalent heterocyclic group bonded to an azo group by a carbon atom.
m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are
It is not at the same time 1H-pyrazol-3-yl. 3. An ink comprising the dye according to claim 2. 4. An ink-jet ink comprising the dye according to claim 2. 5. An ink-jet recording method, wherein recording is performed using the ink-jet ink according to claim 4. 6. A compound represented by the following general formula (II-1) or (II-
A compound represented by 2). Embedded image In the general formulas (II-1) and (II-2),
M ¹ and M ² represent a metal ion. Q ¹ and Q ² are an atomic group forming a heterocyclic group represented by A in the following general formula (I). L represents a ligand coordinated to the metal ion. z represents an integer of 0 or more, and is determined to be a unique number by a metal ion. m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. B represents a monovalent heterocyclic group bonded to the azo group via a carbon atom. Embedded image In the general formula (I), A and B each independently represent
Represents a monovalent heterocyclic group bonded to an azo group by a carbon atom.
m and n each independently represent 0 or 1. M represents a hydrogen atom or a monovalent cation. However, A and B are
It is not at the same time 1H-pyrazol-3-yl.