JP2014101486A - Dye, composition and colored body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye excellent in print density and light resistance and especially suitable for inkjet recording, an ink composition containing the dye, a recording method using the ink composition and a colored body colored by the dye or the ink composition.SOLUTION: There is provided a dye represented by the formula (1) or a salt thereof, or a mixture thereof. In the formula (1), n is an integer of 0 to 5, R, R, Rand Rrepresent each independently a hydrogen atom, an alkyl group, an aryl alkyl group, a halogen atom and the like.

Description

  The present invention relates to a coloring matter, a coloring composition containing the coloring matter, and a colored body colored with the coloring matter.

In recent years, dyes are actively used in color image recording (specifically, ink jet recording, thermal transfer recording, electrophotographic recording, transfer-type silver halide photosensitive recording, printing, recording pen, etc.). Also, in imaging devices, dyes are used as color filters for recording and reproducing full-color images in image sensors such as CCDs, displays such as LCDs (liquid crystal displays) and PDPs (plasma display panels), and the like.
As a method for recording and reproducing a full-color image, an additive color mixture method, a subtractive color mixture method, and the like are known, and three primary color pigments are selected and used from dyes and pigments. However, a dye having optical characteristics capable of expressing a target color reproduction range and having sufficient fastness under various conditions such as use and environment has not been made. For this reason, improvement of the dye itself is still strongly desired.

As one of inks used for ink jet recording, there is an aqueous ink in which a water-soluble dye is dissolved in an aqueous medium. The performance of the water-based ink is to provide a recording image having a sufficient density; no clogging of the discharge nozzle; good drying on the recording material; little bleeding; excellent storage stability ; Etc. are required.
In addition, when ink-jet recording a full-color image or character information expressed on a computer color display, it is desirable that it can be recorded on a recording material with a color tone as faithful as possible. For that purpose, it is desirable that the inks of the three primary colors yellow (Y), magenta (M), and cyan (C) used in ink jet recording have hues that are as close to the respective standards as possible and are clear.
Furthermore, images obtained by inkjet recording are required to have image fastness such as water resistance, moisture resistance, light resistance and gas resistance (including SOx, NOx, and particularly active gases such as ozone gas). .

  Patent Document 1 discloses a light-emitting element containing a compound having a trifluoromethylcarbonyl group.

JP 2003-317964 A

  The present invention is excellent in printing density and light resistance, and is particularly colored by a dye suitable for inkjet recording, an ink composition containing the dye, a recording method using the ink composition, and the dye or ink composition The purpose is to provide a colored body.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific dye represented by the following formula (1) or a salt thereof, or a mixture thereof as a dye, The present invention has been completed.
That is, the present invention relates to the following [1] to [18].
[1]
The pigment | dye represented by following formula (1), its salt, or mixtures thereof.

(In formula (1), n represents an integer of 0 to 5, and R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent.)
[2]
R ¹ , R ² , R ³ , and R ⁴ in the formula (1) are each independently 1 to 3 selected from a hydrogen atom; an alkyl group; a nitrogen atom, an oxygen atom, and a sulfur atom as ring-constituting atoms. A 5- or 6-membered heterocyclic amino group containing an atom; a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms; A condensed 5- or 6-membered heterocyclic amino group condensed with one benzene ring; alkoxy group; aryloxy group; alkylcarbonylamino group; carbamoyl group; hydroxy group; alkylsulfonyl group; arylthio group; The dye or salt thereof, or a mixture thereof according to the above [1], which is a group selected from the group consisting of amino group; arylamino group; halogen atom;
However, the dye represented by the formula (1) or a salt thereof, or a mixture thereof may further have an ionic hydrophilic group as a substituent.
[3]
The dye or a salt thereof, or a mixture thereof according to the above [1] or [2], wherein R ⁴ in the formula (1) is a halogen atom or an arylamino group which may have a substituent.
[4]
The dye or a salt thereof according to the above [1] to [3], wherein R ⁴ in the formula (1) is a halogen atom or an arylamino group having at least one ionic hydrophilic group as a substituent, Or a mixture thereof.
[5]
In the formula (1), n is 0, R ¹ is an alkyl group, R ² and R ³ are hydrogen atoms, and R ⁴ is at least one ionicity as a halogen atom or a substituent. The dye or the salt thereof or the mixture thereof according to [1], which is an arylamino group having a hydrophilic group.
[6]
The ink composition containing the pigment | dye represented by Formula (1) as described in any one of said [1] thru | or [5], its salt, or mixtures thereof, and water.
[7]
The ink composition according to [6], further including a water-soluble organic solvent.
[8]
The content of the inorganic impurities contained in the total mass of the pigment represented by the formula (1) or a salt thereof, or a mixture thereof is 1 with respect to the total mass of the pigment, a salt thereof, or a mixture thereof. The ink composition according to the above [6] or [7], which is not more than mass%.
[9]
Any of [6] to [8] above, wherein the content of the dye represented by the formula (1) or a salt thereof, or a mixture thereof is 0.1 to 20% by mass with respect to the total mass of the ink composition. The ink composition according to claim 1.
[10]
The ink composition according to any one of [6] to [9], which is used for inkjet recording.
[11]
An ink jet recording method for performing recording by ejecting droplets of the ink composition according to [10] according to a recording signal and attaching the droplets to a recording material.
[12]
The inkjet recording method according to [11], wherein the recording material is an information transmission sheet.
[13]
The inkjet recording method according to [12], wherein the information transmission sheet is plain paper or a sheet having an ink receiving layer containing a porous white inorganic substance.
[14]
The colored body colored with the pigment | dye as described in any one of said [1] thru | or [5], its salt, or mixtures thereof.
[15]
A colored body colored with the ink composition according to any one of [6] to [10].
[16]
A colored body colored by the inkjet recording method according to any one of [11] to [13].
[17] An ink jet printer loaded with a container containing the ink composition according to [10].
[18]
By heating the compound represented by the following formula (103) in fuming sulfuric acid at a temperature of 80 ° C. or higher, the dye represented by the formula (1) described in the above [1] or a salt thereof, or a mixture thereof is obtained. How to manufacture.

(In the formula (103), n, R ¹ , R ² , R ³ and R ⁴ all have the same meaning as in the formula (1) described in the above [1].)

  According to the present invention, a coloring matter excellent in printing density and light resistance, particularly suitable for inkjet recording, an ink composition containing the same, a recording method using the ink composition, and a colored body colored with the coloring matter or the ink composition Was able to provide.

The present invention will be described in detail.
In the present specification, in order to avoid complication, in the following, the formula (1) includes all of the “dye or a salt thereof, or a mixture thereof” represented by the formula (1) unless otherwise specified. The “pigment” represented by the above is simply described and has the meaning including all of them.

  The dye of the present invention can express a wide hue from yellow to blue by selecting the type of substituent and the like, and is represented by the formula (1).

  In formula (1), n represents an integer of 0 to 5. Preferably it is 0-4, More preferably, it is 0-3, More preferably, it is 0-2, Most preferably, it is 0.

R ¹ , R ² , R ³ and R ⁴ (hereinafter sometimes referred to as “R ^{1 to} R ⁴ ”) each independently represent a hydrogen atom or a substituent.

The dye represented by the formula (1) has an ionic hydrophilic property selected from the group consisting of a sulfo group, a carboxy group, a phospho group [—P (O) (OH) ₂ group], and a quaternary ammonium group in the molecule. It may have a sex group. In these, a sulfo group and / or a carboxy group are preferable, and a sulfo group is more preferable.
The number of the ionic hydrophilic groups is usually 1 to 5, preferably 1 to 3, more preferably 1 or 2, and further preferably 2. It is preferable to have at least one of these ionic hydrophilic groups.

R ¹ ~ R ^Four Examples of the substituent in include the following.
That is,
A linear, branched or cyclic alkyl group, preferably a C1-C10 alkyl group (specific examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Straight chain such as octyl, n-nonyl, n-decyl; isopropyl, isobutyl, sec-butyl, t-butyl, isoamyl, t-amyl, isohexyl, t-hexyl, isoheptyl, t-heptyl, isooctyl, t-octyl Branched chain (preferably C3-C10) such as 2-ethylhexyl, isononyl, isodecyl; cyclic (preferably C3-C7) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; preferably linear Or a branched chain, more preferably a straight chain.);
An aryl group, preferably a C6-C12 aryl group (specific examples include phenyl, naphthyl, biphenyl and the like);
An arylalkyl group, preferably a C6-C12 aryl C1-C10 alkyl group, more preferably a phenyl C1-C6 alkyl group, still more preferably a phenyl C1-C4 alkyl group (specific examples include phenylmethyl, 2-phenylethyl, 3- The alkyl moiety such as phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and 5-phenylhexyl is linear; the alkyl moiety such as α-methylbenzyl is branched; and the like.
A 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom (preferably an aromatic heterocyclic moiety. Specific examples include: 5-membered cycloaliphatic such as pyrrolidinyl, tetrahydrofuryl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl; 6-membered cycloaliphatic such as piperidinyl, piperazinyl, dioxan-2-yl, morpholinyl, thiomorpholinyl Aromatic 5-membered rings such as pyrrole, pyrazole, imidazole, triazole, furyl, thiophen-2-yl, thiophen-3-yl, oxazole, thiazole, etc .; Aromatic 6-membered rings such as pyridine, pyrazine, pyridazine, triazine In the above, the ring-constituting atom is a nitrogen atom, and Preferably selected from sulfur atom;
A 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as a ring-constituting atom (preferably an aromatic heterocyclic moiety. Specific examples include 5-membered cycloaliphatic amino such as pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, tetrahydrothiophen-3-ylamino; piperidinylamino, piperazinylamino, dioxan-2-ylamino, 6-membered alicyclic compounds such as morpholinylamino, thiomorpholinylamino; pyrroleamino, pyrazoleamino, imidazoleamino, triazoleamino, furylamino, thiophen-2-ylamino, thiophen-3-ylamino, oxazoleamino, Aromatic 5-membered ring such as thiazoleamino; pyridylamino Aromatic six-membered rings such as pyrazylamino, pyridazinylamino, triazinylamino, etc.), etc.), wherein the ring constituent atoms are selected from nitrogen atoms and sulfur atoms Is preferred;
A condensed 5- or 6-membered ring in which one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms A heterocyclic amino group of the ring (preferably the heterocyclic moiety is aromatic. Specific examples include a 5-membered alicyclic heterocyclic moiety such as phthalanylamino; a 6-membered heterocyclic moiety such as benzopyranylamino; Alicyclic ones: benzpyrrololamino, benzpyrazoleamino, benzimidazolamino, benzotriazoleamino, benzofuranylamino, benzothiophen-2-ylamino, benzothiophen-3-ylamino, benzoxazoleamino, benzothiazoleamino, etc. In which the heterocyclic moiety is an aromatic 5-membered ring; quinolinylamino, cinnolinylamino, phthalazinylamino, quinazolinyl A heterocyclic moiety such as mino, quinoxalinylamino and the like having an aromatic 6-membered ring; etc.), and among them, the ring-constituting atom is selected from a nitrogen atom and a sulfur atom. preferable;
Linear, branched or cyclic alkoxy groups, preferably C1-C10 alkoxy groups (specific examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n- Straight chain such as octyloxy, n-nonyloxy, n-decyloxy; isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t- Branched chain (preferably C3-C10) such as octyloxy, 2-ethylhexyloxy, isononyloxy, isodecyloxy; cyclic such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptoxy (preferably C3- 7) ones; preferably include a straight-chain or branched-chain).;
An aryloxy group, preferably a C6-C12 aryloxy group (specific examples include phenoxy, naphthyloxy, biphenyloxy and the like);
A linear, branched or cyclic alkylcarbonylamino group, preferably a C1-C10 alkylcarbonylamino group (specific examples include methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n- Straight chain such as pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n-nonylcarbonylamino, n-decylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butyl Carbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, isohexylcarbonylamino, t-hexylcarbonylamino, isoheptylcal A branched chain (preferably C3-C10) such as nylamino, t-heptylcarbonylamino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino; cyclopropyl Cyclic (preferably C3-C7) such as carbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino; preferably linear or branched, more preferably linear );
An arylcarbonylamino group, preferably a C6-C12 arylcarbonylamino group (specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, etc.);
A linear, branched or cyclic alkylcarbonyloxy group, preferably a C1-C10 alkylcarbonyloxy group (specific examples include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n- Linear chain such as pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, n-decylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butyl Carbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, isohexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcal A branched chain (preferably C3-C10) such as nyloxy, t-heptylcarbonyloxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy; cyclopropyl Cyclic (preferably C3-C7) such as carbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy; preferably linear or branched, more preferably linear );
An arylcarbonyloxy group, preferably a C6-C12 arylcarbonyloxy group (specific examples include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like);
Linear, branched or cyclic alkylcarbonyl group, preferably C1-C10 alkylcarbonyl group (specific examples include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, n-hexyl) Straight chain such as carbonyl, n-heptylcarbonyl, n-octylcarbonyl, n-nonylcarbonyl, n-decylcarbonyl; isopropylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl, isoamylcarbonyl, t-amylcarbonyl , Isohexylcarbonyl, t-hexylcarbonyl, isoheptylcarbonyl, t-heptylcarbonyl, isooctylcarbonyl, t-octylcarbonyl, 2-ethylhexylcarbonyl, isononyl A branched chain (preferably C3-C10) such as rubonyl, isodecylcarbonyl; a cyclic group (preferably C3-C7) such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl; Is linear or branched, more preferably linear));
An arylcarbonyl group, preferably a C6-C12 arylcarbonyl group (specific examples include phenylcarbonyl (benzoyl), naphthylcarbonyl, biphenylcarbonyl, etc.);
A carbamoyl group;
A linear, branched or cyclic monoalkylcarbamoyl group, preferably a mono C1-C10 alkylcarbamoyl group (specific examples include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n-butylcarbamoyl, n-pentylcarbamoyl, n -Hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl and the like; isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, t-butylcarbamoyl, isoamylcarbamoyl, t- Amylcarbamoyl, isohexylcarbamoyl, t-hexylcarbamoyl, isoheptylcarbamoyl, t-heptylcarbamoyl, isooctylcarbamoyl, t-octy A branched chain (preferably C3-C10) such as carbamoyl, 2-ethylhexylcarbamoyl, isononylcarbamoyl, isodecylcarbamoyl; cyclic such as cyclopropylcarbamoyl, cyclobutylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, cycloheptylcarbamoyl Is preferably C3-C7); preferably linear or branched, and more preferably linear));
Linear, branched or cyclic dialkylcarbamoyl group, preferably diC1-C10 alkylcarbamoyl group (specific examples include dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, di-n -Straight chain such as pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di-n-nonylcarbamoyl, di-n-decylcarbamoyl; diisopropylcarbamoyl, diisobutylcarbamoyl, Di-sec-butylcarbamoyl, di-t-butylcarbamoyl, diisoamylcarbamoyl, di-t-amylcarbamoyl, diisohexylcarbamoyl, di-t-hexylcarbamoyl, diisoheptylcarbamoyl, di- -Branched chains such as heptylcarbamoyl, diisooctylcarbamoyl, di-t-octylcarbamoyl, di- (2-ethylhexyl) carbamoyl, diisononylcarbamoyl, diisodecylcarbamoyl (preferably having two C3-C10 branched chains) Cyclic (preferably having two C3-C7 cyclic groups) such as dicyclopropylcarbamoyl, dicyclobutylcarbamoyl, dicyclopentylcarbamoyl, dicyclohexylcarbamoyl, dicycloheptylcarbamoyl; preferably linear or branched , More preferably a linear one).
A monoarylcarbamoyl group, preferably a monoC6-C12 arylcarbamoyl group (specific examples include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl and the like);
A diarylcarbamoyl group, preferably a diC6-C12 arylcarbamoyl group (specific examples include diphenylcarbamoyl, dinaphthylcarbamoyl, di (biphenyl) carbamoyl, etc.);
A linear, branched or cyclic alkoxycarbonyl group, preferably a C1-C10 alkoxycarbonyl group (specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n- Straight chain such as hexyloxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl; isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl , Isoamyloxycarbonyl, t-amyloxycarbonyl, isohexyloxycarbonyl, t-hexyloxycarbonyl, isoheptoxycarbonyl, t-heptoxycarbonyl, isooctyloxycarbonyl, A branched chain (preferably C3-C10) such as octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isononyloxycarbonyl, isodecyloxycarbonyl; cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohexyloxy Cyclic (preferably C3-C7) such as carbonyl and cycloheptoxycarbonyl; preferably linear or branched, more preferably linear).
An aryloxycarbonyl group, preferably a C6-C12 aryloxycarbonyl group (specific examples include phenoxycarbonyl, naphthyloxycarbonyl, biphenyloxycarbonyl and the like);
A linear, branched or cyclic alkylsulfonylamino group, preferably a C1-C10 alkylsulfonylamino group (specific examples include methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n- Straight chain such as pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, n-decylsulfonylamino; isopropylsulfonylamino, isobutylsulfonylamino, sec-butyl Sulfonylamino, t-butylsulfonylamino, isoamylsulfonylamino, t-amylsulfonylamino, isohexylsulfonylamino, t-hexylsulfonylamino, isoheptylsulfur A branched chain (preferably C3-C10) such as nylamino, t-heptylsulfonylamino, isooctylsulfonylamino, t-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononylsulfonylamino, isodecylsulfonylamino; cyclopropyl Cyclic (preferably C3-C7) such as sulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, cycloheptylsulfonylamino; preferably linear or branched, more preferably linear );
An arylsulfonylamino group, preferably a C6-C12 arylsulfonylamino group (specific examples include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino, etc.);
A sulfamoyl group;
A linear, branched or cyclic monoalkylsulfamoyl group, preferably a mono-C1-C10 alkylsulfamoyl group (specific examples include methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, n Linear chain such as -butylsulfamoyl, n-pentylsulfamoyl, n-hexylsulfamoyl, n-heptylsulfamoyl, n-octylsulfamoyl, n-nonylsulfamoyl, n-decylsulfamoyl Isopropylsulfamoyl, isobutylsulfamoyl, sec-butylsulfamoyl, t-butylsulfamoyl, isoamylsulfamoyl, t-amylsulfamoyl, isohexylsulfamoyl, t-hexylsulfa Moyl, isoheptylsulfamoyl, t-heptylsulfa Of branched chains (preferably C3-C10) such as yl, isooctylsulfamoyl, t-octylsulfamoyl, 2-ethylhexylsulfamoyl, isononylsulfamoyl, isodecylsulfamoyl; Cyclic (preferably C3-C7) such as moyl, cyclobutylsulfamoyl, cyclopentylsulfamoyl, cyclohexylsulfamoyl, cycloheptylsulfamoyl; preferably linear or branched, more preferably straight Chain));
A linear, branched or cyclic dialkylsulfamoyl group, preferably a diC1-C10 alkylsulfamoyl group (specific examples include dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, Di-n-butylsulfamoyl, di-n-pentylsulfamoyl, di-n-hexylsulfamoyl, di-n-heptylsulfamoyl, di-n-octylsulfamoyl, di-n-no Straight chain such as nylsulfamoyl, di-n-decylsulfamoyl; diisopropylsulfamoyl, diisobutylsulfamoyl, di-sec-butylsulfamoyl, di-t-butylsulfamoyl, diisoamylsulfa Moyl, di-t-amylsulfamoyl, diisohexylsulfamoyl, di-t-hexylsulfa Yl, diisoheptylsulfamoyl, di-t-heptylsulfamoyl, diisooctylsulfamoyl, di-t-octylsulfamoyl, di- (2-ethylhexyl) sulfamoyl, diisononylsulfamoyl, diisodecylsulfur A branched chain such as famoyl (preferably having two C3-C10 branched chains); dicyclopropylsulfamoyl, dicyclobutylsulfamoyl, dicyclopentylsulfamoyl, dicyclohexylsulfamoyl, dicyclo Cyclic (preferably having two C3-C7 cyclic groups) such as heptylsulfamoyl; preferably linear or branched, more preferably linear).
A monoarylsulfamoyl group, preferably a mono C6-C12 arylsulfamoyl group (specific examples include phenylsulfamoyl, naphthylsulfamoyl, biphenylsulfamoyl and the like);
A diarylsulfamoyl group, preferably a diC6-C12 arylsulfamoyl group (specific examples include diphenylsulfamoyl, dinaphthylsulfamoyl, di (biphenyl) sulfamoyl and the like);
A hydroxy group;
Linear, branched or cyclic alkylsulfonyl group, preferably C1-C12 alkylsulfonyl group (specific examples include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, n-hexyl) Straight chain such as sulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecylsulfonyl, n-dodecylsulfonyl; isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t -Butylsulfonyl, isoamylsulfonyl, t-amylsulfonyl, isohexylsulfonyl, t-hexylsulfonyl, isoheptylsulfonyl, t-heptylsulfonyl, isooctylsulfonyl, t-octyls A branched chain (preferably C3-C12) such as phonyl, 2-ethylhexylsulfonyl, isononylsulfonyl, isodecylsulfonyl, isoundecylsulfonyl, t-undecylsulfonyl, isododecylsulfonyl, t-dodecylsulfonyl, etc .; cyclopropyl Cyclic (preferably C3-C7) such as sulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl; preferably linear or branched, more preferably linear. ;
An arylsulfonyl group, a C6-C12 arylsulfonyl group (specific examples include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl and the like);
Linear, branched or cyclic alkylthio group, preferably C1-C10 alkylthio group (specific examples include methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n- Straight chain such as octylthio, n-nonylthio, n-decylthio; isopropylthio, isobutylthio, sec-butylthio, t-butylthio, isoamylthio, t-amylthio, isohexylthio, t-hexylthio, isoheptylthio, t-heptylthio, One having a branched chain (preferably C3-C10) such as isooctylthio, t-octylthio, 2-ethylhexylthio, isononylthio, isodecylthio; cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclohexane Cyclic such Chiruchio (preferably C3-C7) ones; those preferably a straight chain or branched chain, or more preferably a straight chain).;
An arylthio group, preferably a C6-C12 arylthio group (specific examples include phenylthio, naphthylthio, biphenylthio and the like);
Ureido group;
A linear, branched or cyclic monoalkylureido group, preferably a mono C1-C10 alkylureido group (specific examples include methylureido, ethylureido, n-propylureido, n-butylureido, n-pentylureido, n A straight chain such as hexylureido, n-heptylureido, n-octylureido, n-nonylureido, n-decylureido; isopropylureido, isobutylureido, sec-butylureido, t-butylureido, isoamylureido, t-amylureido, Branched chains such as isohexylureido, t-hexylureido, isoheptylureido, t-heptylureido, isooctylureido, t-octylureido, 2-ethylhexylureido, isononylureido, isodecylureido, etc. C3-C10); cyclic (preferably C3-C7) such as cyclopropylureido, cyclobutylureido, cyclopentylureido, cyclohexylureido, cycloheptylureido, etc .; preferably linear or branched Preferably a straight chain is mentioned.);
Linear, branched or cyclic dialkylureido groups, preferably diC1-C10 alkylureido groups (specific examples include dimethylureido, diethylureido, di-n-propylureido, di-n-butylureido, di-n -Straight chain such as pentylureido, di-n-hexylureido, di-n-heptylureido, di-n-octylureido, di-n-nonylureido, di-n-decylureido; diisopropylureido, diisobutylureido, di- sec-butylureido, di-t-butylureido, diisoamylureido, di-t-amylureido, diisohexylureido, di-t-hexylureido, diisoheptylureido, di-t-heptylureido, diisooctylureido , Di-t-octylureido, di- (2-e Ruhexyl) having a branched chain such as ureido, diisononylureido, diisodecylureido (preferably having two C3-C10 branched chains); dicyclopropylureido, dicyclobutylureido, dicyclopentylureido, dicyclohexylureido, dicycloheptyl Cyclic (preferably having two C3-C7 cyclic groups) such as ureido; preferably linear or branched, more preferably linear).
A monoarylureido group, preferably a mono C6-C12 arylureido group (specific examples include phenylureido, naphthylureido, biphenylureido, etc.);
A diarylureido group, preferably a diC6-C12 arylureido group (specific examples include diphenylureido, dinaphthylureido, di (biphenyl) ureido, etc.);
A linear, branched or cyclic alkoxycarbonylamino group, preferably a C1-C10 alkoxycarbonylamino group (specific examples include methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, n- Straight chain such as pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octyloxycarbonylamino, n-nonyloxycarbonylamino, n-decyloxycarbonylamino; isopropoxycarbonylamino, Isobutoxycarbonylamino, sec-butoxycarbonylamino, t-butoxycarbonylamino, isoamyloxycarbonylamino, t-amyloxycarbonylamino, isohexyloxycarbonyla , T-hexyloxycarbonylamino, isoheptoxycarbonylamino, t-heptoxycarbonylamino, isooctyloxycarbonylamino, t-octyloxycarbonylamino, 2-ethylhexyloxycarbonylamino, isononyloxycarbonylamino, iso Branched chain such as decyloxycarbonylamino (preferably C3-C10); cyclic such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, cycloheptoxycarbonylamino (preferably C3-C7); preferably linear or branched, more preferably linear));
An aryloxycarbonylamino group, preferably a C6-C12 aryloxycarbonylamino group (specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, etc.);
A cyano group;
A nitro group;
An amino group;
A linear, branched or cyclic monoalkylamino group, preferably a mono C1-C10 alkylamino group (specific examples include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n Straight chain such as -hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino; isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, Branched chain such as isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-octylamino, 2-ethylhexylamino, isononylamino, isodecylamino (preferably C3-C10) Cyclopropylamino, Robuchiruamino, cyclopentylamino, those cyclohexylamino, annular, etc. cycloheptylamino (preferably C3-C7); those preferably a straight chain or branched chain, or more preferably a straight chain).;
A linear, branched or cyclic dialkylamino group, preferably a diC1-C10 alkylamino group (specific examples include dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n- Straight chain such as pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, di-n-decylamino; diisopropylamino, diisobutylamino, di-sec -Butylamino, di-t-butylamino, diisoamylamino, di-t-amylamino, diisohexylamino, di-t-hexylamino, diisoheptylamino, di-t-heptylamino, diisooctylamino, Di-t-octylamino, di- (2-ethylhexyl) amino, diisononylamino, diiso A branched chain such as silamino (preferably having two C3-C10 branched chains); cyclic such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, etc. (preferably C3 -C7 cyclic groups); preferably linear or branched, more preferably linear.);
A mono C6-C12 arylamino group (specific examples include phenylamino (anilino), naphthylamino, biphenylamino, etc.) as an arylamino group (monoarylamino group or diarylamino group, preferably monoC6-C12 arylamino group) );
Similarly, as the arylamino group, a di-C6-C12 arylamino group (specific examples include diphenylamino, dinaphthylamino, di (biphenyl) amino and the like);
A mercapto group (in the present specification, a group represented by "-SH");
A halogen atom (specific examples include a fluorine atom, a chlorine atom and a bromine atom; preferably a fluorine atom, a chlorine atom and a bromine atom);

The above substituents for R ^{1 to} R ⁴ may further have one or two, preferably one, selected from these substituents.
In particular, with respect to the ionic hydrophilic group, the substituents in R ^{1 to} R ⁴ other than the ionic hydrophilic group are preferably further included. The number of ionic hydrophilic groups at that time is as described above.

Among the above, R ^{1 to} R ⁴ are each a hydrogen atom; an alkyl group; an arylalkyl group; a ring component atom containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom. A heterocyclic amino group of the ring; one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as ring constituent atoms A condensed 5- or 6-membered heterocyclic amino group; alkoxy group; aryloxy group; alkylcarbonylamino group; carbamoyl group; hydroxy group; alkylsulfonyl group; arylthio group; cyano group; Atoms are preferred.

Among the above, R ¹ is preferably a hydrogen atom, an alkyl group or an arylalkyl group, more preferably a hydrogen atom or a linear, branched or cyclic C1-C10 alkyl group, and a hydrogen atom or a linear C1-C6 alkyl group. The group is more preferable, and among them, a C1-C4 alkyl group, particularly a methyl group is preferable.

Of the above, R ² is preferably a hydrogen atom.

Among the above, R ³ is preferably a hydrogen atom or an aryloxy group, more preferably a hydrogen atom.
Examples of the aryloxy group include C6-C12, preferably C6-C10 aryloxy group. Among these, a phenoxy group is preferable, and a phenoxy group having a group selected from the group consisting of an alkyl group and an ionic hydrophilic group (preferably a carboxy group or a sulfo group, more preferably a carboxy group) is more preferable as a substituent. preferable. The alkyl group is preferably the same as the alkyl group mentioned as the “substituent in R ^{1 to} R ⁴ ”, and among them, a branched chain is more preferable.
When R ³ has the above-mentioned “substituent in R ^{1 to} R ⁴ ”, preferably an aryloxy group, the substitution position is not particularly limited. However, in the formula (1), in the ring portion where both the nitrogen atom having R ¹ as a substituent and R ⁴ are substituted, the former substitution position is the 1st position and the latter substitution position is the 4th position clockwise. In particular, it is particularly preferred that the substitution position of R ³ is the 2-position.

Among the above, R ⁴ is a 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as a ring atom; a nitrogen atom as a ring atom; A condensed 5- or 6-membered heterocyclic amino group in which one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from an oxygen atom and a sulfur atom; Aryloxy group; hydroxy group; arylthio group; amino group; arylamino group; halogen atom; Among these groups, those having an aryl or heterocyclic ring include an alkyl group; an alkoxy group; an alkylcarbonylamino group; a carbamoyl group; an alkylsulfonyl group; a cyano group; A group selected from the group consisting of a group; a halogen atom;
Among the above, R ⁴ is an aryloxy group; a 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom; A condensed 5- or 6-membered ring in which one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom. More preferred are a heterocyclic amino group; a hydroxy group; an arylthio group; an amino group; an arylamino group; or a halogen atom.
Examples of the aryloxy group include the same ones as described above, and phenoxy is preferable.
The 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as the ring constituent atom is one selected from a nitrogen atom and a sulfur atom, or Those containing two atoms are preferred, and among them, those having a heterocyclic portion of an aromatic 5-membered ring, specifically, thiophen-2-ylamino, thiazol-2-ylamino and the like are preferred.
A condensed ring type 5 or 6 in which one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as the ring constituent atoms The membered heterocyclic amino group preferably contains one nitrogen atom and one sulfur atom, and benzothiazol-2-ylamino and the like are particularly preferable.
Examples of the arylthio group include the same ones as described above, and phenylthio is preferable.
Examples of the arylamino group include the same arylamino groups as those described above as the “substituents in R ^{1 to} R ⁴ ”, including the preferable ones. Monoarylamino groups are preferable, and phenylamino or naphthylamino is more preferable. Preferably, phenylamino is more preferable. In addition, the substituent of the aryl moiety is preferably a group selected from the same group as described above; among these groups, an alkyl group, an alkoxy group, an alkylcarbonylamino group, an alkylsulfonyl group, a carbamoyl group, an arylsulfonylamino group , A cyano group, an amino group, and a halogen atom are more preferable; an alkyl group, an alkoxy group, an alkylcarbonylamino group, an arylsulfonylamino group, an amino group, and a halogen atom (in this case, a fluorine atom or a chlorine atom are more preferable) preferable. The arylamino group is more preferably an arylamino group having at least one ionic hydrophilic group (substituted with at least one ionic hydrophilic group), and a monophenylamino group substituted with two sulfo groups (Anilino group substituted by two sulfo groups) is particularly preferred. In addition, preferable examples of the substituent for the aryl moiety include an arylcarbonylamino group having at least one ionic hydrophilic group. Examples of the arylcarbonylamino group include the same arylcarbonylamino groups as those described above as the “substituents for R ^{1 to} R ⁴ ”, and among them, a phenylcarbonylamino group or a naphthylcarbonylamino group can be mentioned. In this case, the ionic hydrophilic group is preferably a carboxy group or a sulfo group, and more preferably a carboxy group. The number of substitutions of these ionic hydrophilic groups is usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
The halogen atom is preferably the same as the halogen atom listed as the “substituent in R ^{1 to} R ⁴ ”, and among them, a bromine atom is more preferable.

Among the above, R ⁴ is preferably an arylamino group having at least one ionic hydrophilic group or a halogen atom. Among the substituents for the aryl moiety of the arylamino group, among them, an alkyl group, an alkoxy group, an alkylcarbonylamino group, an arylsulfonylamino group, an amino group, an arylcarbonylamino group having at least one ionic hydrophilic group, and Groups selected from the group consisting of halogen atoms are preferred, and among these, groups selected from the group consisting of alkyl groups, alkoxy groups, alkylcarbonylamino groups, arylsulfonylamino groups, and amino groups are more preferred.

Among the above, when R ⁴ is an arylamino group having at least one ionic hydrophilic group, the number of substituents of the aryl moiety other than the ionic hydrophilic group is usually 1 or 2, preferably 1. One.

In the above-mentioned “substituents in R ^{1 to} R ⁴ ” and groups, substitution positions, etc. individually listed as R ¹ , R ² , R ³ and R ⁴ , preferred combinations are more preferred, and more preferred are The combination of is more preferable. The same applies to a combination of a preferable one and a more preferable one, and a combination of a more preferable one and a more preferable one.

The salt of the dye represented by the formula (1) means a salt formed with an inorganic or organic cation. Preferred examples of salts formed with inorganic cations include salts formed with alkali metals such as lithium, sodium and potassium cations; or ammonium (NH ₄ ⁺ ).
Preferable examples of salts formed with organic cations include salts formed with organic ammonium represented by the following formula (2).

In formula (2), Z _{1 to} Z ₄ each independently represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a hydroxyalkoxyalkyl group, and at least one of Z _{1 to} Z ₄ is a group other than a hydrogen atom. is there.

In formula (2), specific examples of Z _{1 to} Z ₄ include C1-C6 alkyl groups (preferably C1-C4 alkyl groups) such as methyl, ethyl, butyl, pentyl, hexyl; hydroxymethyl, 2-hydroxyethyl Hydroxy C1-C6 alkyl groups (preferably hydroxy C1-C4 alkyl groups) such as 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl; Hydroxy C1-C6 alkoxy C1-C6 alkyl groups (preferably hydroxy C1-C4 alkoxy C1-C4 alkyl groups) such as hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl; Can be mentioned.

  Of these, more preferred are salts formed with cations such as sodium, potassium, lithium, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and ammonium. . Among these, lithium, ammonium and sodium salts are particularly preferable.

The salt of the dye represented by the formula (1) may be any of a single salt, a plurality of kinds of mixed salts, or a mixture of a free acid and a salt. The dye represented by the formula (1) may change the physical properties such as solubility, or the performance of the ink containing the compound, particularly the performance related to fastness, depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the performance of the target ink.
Methods for producing various salts from free acids; methods for obtaining free acids from various salts; methods for exchanging salts from specific salts to other salts; Can be used.

Although the specific example of the pigment | dye represented by this said Formula (1) is shown in following Table 1, this invention is not limited to these specific examples.
In the tables, n, and ^R 1 to R ⁴ correspond to ^R 1 to R ⁴ in Formula (1).

The meanings of abbreviations and the like in the table are as follows.
H: A hydrogen atom.
Me: methyl group.
Ph: phenyl group.
SO ₃ H: a sulfo group.
CO ₂ H: Carboxy group.
CONH _2: carbamoyl group.
OMe: Methoxy group.
CN: cyano group.
Cl: chlorine atom.
Br: Bromine atom.
F: A fluorine atom.
SO ₂ Hex: Hexylsulfonyl group.
SO ₂ Me: methylsulfonyl group.
Ac: Acetyl group.
Ts: p-toluenesulfonyl group

The method for producing the dye represented by the formula (1) is described below. In addition, R < ¹ > -R < ⁴ > and n as described in following formula (101)-(103) represent the same meaning as the said Formula (1). The number of moles of the compound described in the production method is a representative example, and those skilled in the art can understand that it can be appropriately increased or decreased as necessary.

In 1 mol of the compound of the following formula (101), 1.1 to 3 mol of the compound represented by the following formula (102) is added at 130 to 180 ° C. in the presence of a basic compound such as sodium carbonate in a polar solvent such as xylene. For 5 to 15 hours to obtain the target compound of the following formula (103). R ¹⁰² in Formula (102) represents an alkyl group (preferably a C1-C6 alkyl group, more preferably a C1-C4 alkyl group), and specifically, methyl or ethyl is preferable. The compound of the formula (102) can also be obtained as a commercial product.

  The obtained compound of the formula (103) is usually 80 ° C. or higher, preferably 80 to 150 ° C., more preferably 80 to 140 ° C., further preferably 80 to 130 ° C., particularly preferably 80 in 5-30% fuming sulfuric acid. By ring-closing at ˜120 ° C., the compound represented by the formula (1) can be obtained.

In the compound of formula (101) or formula (103) and the dye represented by formula (1), when R ⁴ is a group having a leaving ability such as a halogen atom, this is used as a leaving group. It is also possible to convert R ⁴ to a group other than a halogen atom by performing a substitution reaction.
As an example, for example, a compound such as R ⁴ is a bromine atom, or a dye such as a base such as sodium carbonate and a copper such as copper acetate in an aprotic polar organic solvent such as N, N-dimethylformamide. In the presence of a catalyst, 1.1 to 3 mol of an arylamine which may have a substituent is reacted at 110 to 150 ° C. for 1 to 60 hours, whereby R ⁴ may have an arylamino which may have a substituent. A compound represented by the formula (101) or the formula (103) as a group or a dye represented by the formula (1) can also be obtained.

  The coloring matter represented by the formula (1) has a small amount of inorganic impurities, such as metal cation chlorides (such as sodium chloride) and sulfates (such as sodium sulfate) contained as impurities in the total mass. Is preferably used. As a guide, for example, the content of inorganic impurities is about 1% by mass or less with respect to the total mass of the dye represented by the formula (1). As a method for producing a pigment having a small amount of inorganic impurities, for example, a known method using a reverse osmosis membrane; Examples include a known method using an ion exchange resin as appropriate;

The ink composition of the present invention contains the dye represented by the formula (1) as a dye, and is dissolved in water or an aqueous solvent (water containing a water-soluble organic solvent described later).
The ink composition usually contains 0.1 to 20% by mass, preferably 1 to 15% by mass, and more preferably 2 to 10% by mass of the dye represented by the formula (1).
In addition, the ink composition contains 0 to 30% by weight, preferably 5 to 20% by weight of a water-soluble organic solvent, and 0 to 10% by weight of an ink preparation agent as components other than the pigment and water, respectively. Also good. The water-soluble organic solvent may have effects such as dissolution of pigment, prevention of drying of the ink composition, adjustment of viscosity, promotion of penetration into the recording material, adjustment of surface tension, defoaming, etc. It is preferable to contain them.

  The ink composition may contain a coloring matter represented by a plurality of formulas (1), for example, for the purpose of (finely) adjusting the hue and print density of the ink composition to a desired one. Moreover, you may contain other well-known pigment | dye in the range which does not inhibit the effect obtained by this invention.

  Examples of the water-soluble organic solvent include C1-C4 alkanols (alcohols) such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide Or a carboxylic acid amide such as N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one Heterocyclic ureas such as; ketones or keto alcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2- or 1, 3 -Propylene glycol, 1,2- or 1, -Mono, oligo or polyalkylene having C2-C6 alkylene units such as butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, thiodiglycol, polyethylene glycol, polypropylene glycol, etc. Glycol or thioglycol; polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol Monomethyl ether or triethylene glycol monoethyl ether C1-C4 alkyl ethers of polyhydric alcohols and the like; .gamma.-butyrolactone; or dimethyl sulfoxide and the like.

Among these, preferred are isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, diethylene glycol monobutyl ether, more preferably isopropanol, glycerin, Examples include diethylene glycol monobutyl ether (butyl carbitol), 2-pyrrolidone, and N-methyl-2-pyrrolidone.
These water-soluble organic solvents may be used alone or in combination.

  Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye dissolving agents, and surfactants.

Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, Benzothiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And benzyl bromacetate compounds.
An example of the organic halogen compound is sodium pentachlorophenol.
Examples of pyridine oxide compounds include sodium 2-pyridinethiol-1-oxide.
Examples of the isothiazoline-based compound include 1,2-benzisothiazoline-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5- Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like It is done.
Other antiseptic and antifungal agents include sodium sorbate, sodium benzoate, anhydrous sodium acetate, and trade names: Proxel ^RTM GXL (S), Proxel ^RTM XL-2 (S), and the like.
In the present specification, the superscript “RTM” means a registered trademark.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of 7.5 to 11.0 without adversely affecting the prepared ink. For example, alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water); or lithium carbonate, sodium carbonate and potassium carbonate And alkali metal carbonates.

  Examples of chelating reagents include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone and sulfonated benzotriazole.

  Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

  Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like.

  Examples of the surfactant include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.

  Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ether sulfates Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfate , Diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives Etc.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene alcohol such as ol; As another example, manufactured by Nissin Chemical Industry Co., Ltd., trade name Surfynol ^RTM 104E, the 104PG50, 82, 465, trade name Olfine ^RTM STG and the like; Etc.
These ink preparation agents may be used alone or in combination.

In the production of the ink composition, the order in which the components contained in the ink composition are dissolved is not particularly limited. The ink preparation agent may be added after the dye is dissolved in water or an aqueous solvent, or the water-soluble organic solvent and the ink preparation agent may be added after the dye is dissolved in water. The order may be different from this.
As the coloring matter contained in the ink composition, for example, in the synthesis step of the coloring matter represented by the formula (1), the coloring matter is isolated by an operation such as crystallization from the reaction solution after completion of the final step; or spray drying; A dried product can be used.
In addition, the reaction solution after completion of the final step; or the aqueous solution obtained by subjecting the aqueous solution containing the dye to a desalting treatment with a reverse osmosis membrane; An ink composition may be produced by adding a solvent, an ink preparation agent, or the like.
The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water or distilled water. The ink composition thus prepared may be subjected to microfiltration using a membrane filter or the like as necessary to remove impurities. When the ink composition is used for ink jet recording, it is preferable to perform microfiltration. The pore diameter of the filter for performing microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

When the dye represented by the formula (1) does not have water solubility, for example, a dispersing agent is used; all or part of the dye surface is coated with a polymer resin to give self-dispersibility; It can also be used as a dispersed ink composition by a known dispersion method.
In the present specification, “water-soluble” means that the dye represented by the formula (1) is usually dissolved in 5 g or more, preferably 10 g or more, more preferably 15 g or more, and further preferably 20 g or more with respect to 1 liter of water. Means that.

In the ink jet recording method of the present invention, a container containing the ink composition of the present invention is loaded in a predetermined position of an ink jet printer, and (small) droplets of the ink composition are ejected according to a recording signal to be recorded. This is a method for recording on a material.
In the ink jet recording method, the ink composition containing the coloring matter represented by the formula (1) can be used alone or as an ink set as yellow to blue ink according to the hue.
On the other hand, for the purpose of obtaining a full-color recorded image, in addition to the ink composition containing the dye represented by the formula (1), for example, the known three primary colors of yellow, magenta, and cyan, or green, orange, red, It is good also as an ink set with the ink composition which added each color, such as violet, blue, and black. At this time, containers containing ink compositions appropriately selected from the above-described colors may be loaded and used at predetermined positions of the ink jet printer.
Since the coloring matter represented by the formula (1) can express a wide range of hues as described above, it can be used as an ink composition of yellow, orange, red, magenta, violet and blue among the above-mentioned colors. Particularly preferred is magenta.

  Examples of the discharge method of the ink jet printer include a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like. The ink composition of the present invention can be used in any ejection system including these systems.

Examples of the recording material include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and a color filter base material.
As the information transmission sheet, a surface-treated sheet, specifically, a substrate (for example, the above-mentioned recording material) provided with an ink receiving layer is preferable. For example, the ink-receiving layer may be impregnated or coated with a cationic polymer on a base material; porous silica, alumina sol, special ceramics, or other porous white inorganic substances capable of adsorbing pigments in ink, such as polyvinyl alcohol or polyvinyl pyrrolidone Coating on the surface of the substrate together with the hydrophilic polymer. A paper provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Examples of commercially available products, for example, (Ltd.) Pictorico Ltd., trade name Pictorico ^RTM professional; manufactured by Canon Inc., trade name Professional Photo Paper, Super Photo Paper, Matte Photo Paper, Epson Co., Ltd. under the trade name Kurisupia ^RTM, photo paper ( Glossy), photo matte paper, Superfine gloss film; Nippon Hewlett-Packard Co., Ltd., product name Advanced Photo Paper, Premium Plus Photo Paper, Premium Gloss Film, Photo Paper; Konica Minolta Photo Imaging Co., Ltd., product Name photo-like QP;
Of course, an information transmission sheet having no ink receiving layer, such as plain paper such as PPC (plain paper copy) paper, can be used as a recording material.

  Examples of the porous white inorganic substance include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, Examples thereof include titanium dioxide, zinc sulfide, and zinc carbonate.

The colored product of the present invention means a substance colored by the dye of the present invention or an ink composition containing the dye. There is no particular limitation on the substance to be colored. As an example, for example, the recording material described above; an ink sheet in a heat-sensitive recording material and a recording material colored by the ink sheet; a color toner for electrophotography and a recording material colored thereby; LCD, PDP, etc. Examples include colored curable resin compositions used for the production of imaging devices such as displays and CCDs, and color filters produced using this resin composition; It is not limited.
Examples of the coloring method include dip dyeing, textile printing, screen printing, ink jet recording, thermal recording, electrophotographic recording, and the like. The colored body of the present invention is preferably a colored body colored by the inkjet recording method of the present invention.

  The ink composition of the present invention has a clear magenta color, has a clear hue particularly on glossy paper, and has high fastness of recorded images. Moreover, it is highly safe for humans.

The dye represented by the formula (1) has an absorption characteristic with excellent color reproducibility and excellent color reproducibility, and has sufficient fastness to light, heat, humidity, and active gases in the environment. . Applications include, for example, inks for printing such as inkjet, ink sheets in heat-sensitive recording materials, color toners for electrophotography, color filters used in displays such as LCDs and PDPs, and image sensors such as CCDs, and for various fibers. Examples of the coloring composition include dyeing solution for dyeing and resin coloring.
The ink composition containing the coloring matter represented by the formula (1) can be used for various recording and printing applications such as printing, copying, marking, writing, drafting, stamping, and the like, particularly for inkjet recording. It is suitably used as an ink. Images recorded on ink jet dedicated paper or glossy paper using this ink composition have high print density, and are excellent in various fastness properties such as water resistance, light resistance, ozone resistance, friction resistance, and moisture resistance. It has a hue suitable for.
The ink composition containing the coloring matter represented by the formula (1) does not precipitate or separate during storage, and has extremely high storage stability. Further, since the coloring matter represented by the formula (1) and having an ionic hydrophilic group in the above range is excellent in water solubility, when an aqueous ink composition containing the coloring matter is used for ink jet recording, a nozzle Solid precipitation due to drying of the ink composition in the vicinity hardly occurs, and the ejector (ink head) is not blocked. Further, the ink composition has physical properties even in usage environments such as use under constant recirculation for a relatively long time in a continuous ink jet printer; or intermittent use in an on-demand ink jet printer. Does not change.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “parts” and “%” are based on mass unless otherwise specified. In addition, the operations such as each reaction and crystallization were performed with stirring unless otherwise specified.
In the examples, the maximum absorption wavelength (λmax) was measured as follows. That is, with respect to the water-soluble dye, the measured value with an ultraviolet-visible spectrophotometer UV-2550 (manufactured by Shimadzu Corporation) was described in an aqueous solution having a pH of 5-8. Moreover, about the pigment | dye other than that, the measurement value by the diode array detector of the Agilent Technology company and the Agilent 1100 Series HPLC System was described. As the mobile phase in the latter measurement, a 5 mM ammonium acetate aqueous solution / acetonitrile solvent system was used.
In addition, when the required amount of the target compound was not obtained in one synthesis reaction, the same synthesis reaction was repeated until the required amount was obtained.

[Example 1]
(Process 1)
In 150 parts of xylene, 63.2 parts of a compound of the formula (3) (can be purchased as a commercial product), 82.8 parts of ethyl 4,4,4-trifluoroacetoacetate, 2.0 parts of sodium bicarbonate, diaza 1.2 parts of bicycloundecene was added, and ethanol and water produced at 140 to 145 ° C. were reacted for 14 hours while azeotroping with xylene and distilling out of the reaction system. The reaction solution was cooled to 80 ° C., 200 parts of methanol was added dropwise, and the precipitated solid was collected by filtration and dried to obtain 85.5 parts of a yellow powder of a compound represented by the following formula (4).

(Process 2)
After adding 30.0 parts of the compound represented by the formula (4) obtained in Example 1 (Step 1) to 230.0 parts of 12.0% fuming sulfuric acid, the mixture was reacted at 90 ° C. for 1 hour. This solution was added to 400 parts of ice water and stirred at room temperature for 20 minutes. The precipitated solid was collected by filtration and washed with 500 parts of water to obtain 145.6 parts of a wet cake. The obtained wet cake was added to 100 parts of methanol and 250 parts of water, and stirred at 60 ° C. for 1 hour. The obtained liquid was cooled to room temperature, neutralized with 25% aqueous sodium hydroxide solution to pH 7.0-8.0, and then the precipitated solid was collected by filtration and dried to obtain the following formula (5). 30.0 parts (λmax: 414 nm) of a yellow powder of the dye of the present invention was obtained.

[Example 2]
In 30 parts of N, N-dimethylformamide, 4.3 parts of the dye of the formula (5) obtained in Example 1 (Step 2), 3.7 parts of aniline, copper (II) acetate monohydrate 1 part and 1.5 parts of sodium acetate were added, and it reacted at 115-120 degreeC for 8 hours. The reaction solution was cooled to 80 ° C., 100 parts of methanol was added dropwise, the precipitated solid was collected by filtration, and dried to obtain 3.1 parts of a red powder of the dye of the present invention represented by the following formula (6) ( (λmax: 534 nm) was obtained.

[Example 3]
After adding 4.5 parts of the pigment | dye represented by Formula (6) obtained in Example 2 to 36.0 parts of 10% fuming sulfuric acid, it reacted at 40-50 degreeC for 3 hours. The obtained solution was added to 100 parts of ice water and stirred at room temperature for 20 minutes. The solid precipitated from this liquid was collected by filtration and washed with 100 parts of water to obtain 11.7 parts of a wet cake. The obtained wet cake was added to 50 parts of ethanol and 15 parts of water, and stirred at room temperature for 1 hour. This solution was neutralized with a 25% aqueous sodium hydroxide solution to pH 7.0-8.0, and the precipitated solid was collected by filtration and dried to obtain an ionic hydrophilic group represented by the following formula (7). Thus, 4.9 parts (λmax: 523 nm) of the dye of the present invention was obtained.

[Example 4]
Example 4 describes another method for synthesizing the dye represented by the formula (7).
(Process 1)
In 265 parts of xylene, 105.1 parts of a compound of the formula (8) (commercially available), 134.6 parts of ethyl 4,4,4-trifluoroacetoacetate, 1.5 parts of diazabicycloundecene In addition, ethanol and water produced by the reaction at 135 ° C. were reacted for 9 hours while azeotropically distilling with xylene and distilling out of the reaction system. The reaction solution was cooled to 60 ° C., 165 parts of methanol was added dropwise and stirred for 1 hour, and then the precipitated solid was collected by filtration and dried to obtain a red powder 106.9 of the compound represented by the following formula (9). Got a part.

(Process 2)
After adding 4.5 parts of the compound represented by the formula (9) obtained in Example 4 (Step 1) to 35.7 parts of 12.0% fuming sulfuric acid under water cooling, the mixture was reacted at 90 ° C. for 12 hours. . This reaction solution was added to 120 parts of ice water. After adding 25 parts of sodium chloride to the obtained liquid, it stirred at room temperature for 1 hour, and stirred at 60 degreeC for 20 minutes. The solid precipitated from this liquid was collected by filtration and washed with 50 parts of a 20% aqueous sodium chloride solution to obtain 10.1 g of a wet cake. The obtained wet cake was added to 200 parts of methanol and suspended and stirred at 60 ° C. for 1 hour, and then the solid was collected by filtration and dried, whereby the dye of the present invention represented by the formula (7) 5. 0 parts (λmax: 523 nm) were obtained.

[Example 5]
[(A) Preparation of Ink Composition]
Using the dye represented by Formula (7) obtained in Example 3 as a dye, the components shown in Table 5 below were mixed and dissolved to prepare a water-based ink composition. The obtained ink composition was filtered through a 0.45 μm membrane filter to remove impurities, and an inkjet ink composition for evaluation test was obtained. The water used for the preparation of the ink composition is ion-exchanged water. After adjusting with a 25% aqueous sodium hydroxide solution so that the pH of the ink composition is about 9.0, water is added so that the total amount becomes 100 parts. added. This ink composition was prepared as Example 5.
In Table 2 below, “Surfinol 104PG50” is a trade name, which is an acetylene glycol nonionic surfactant manufactured by Nissin Chemical.

[Comparative Example 1]
In Example 4 (Step 2), a comparative compound represented by the following formula (10) was obtained in the same manner as in Example 4 except that the reaction temperature in fuming sulfuric acid was changed from 90 ° C. to 50 ° C. It was.
A comparative aqueous inkjet ink composition was prepared in the same manner as in Example 5 except that the following formula (10) was used as a dye instead of the dye represented by the formula (7). This ink preparation is referred to as Comparative Example 1.

[(B) Inkjet recording]
By performing ink jet recording on each of the ink compositions prepared in Example 5 and Comparative Example 1 on 5 types of glossy paper and 1 type of plain paper using an ink jet printer (trade name: PIXUS ^RTM ip4500 manufactured by Canon Inc.). A record was obtained. During ink jet recording, an image pattern was prepared so that the reflection density was obtained in several levels of gradation, and a recorded matter having gradation was obtained. The obtained recorded matter was used as a test piece, and various tests were performed.
As recording materials for inkjet recording, the following glossy papers 1 to 5 and plain paper 1 were used.
Glossy paper 1:
Product name: Canon Photographic Paper, Platinum Grade, manufactured by Canon Inc.
Glossy paper 2:
Product name: Canon Photographic Paper / Glossy Gold, manufactured by Canon Inc.
Glossy paper 3:
Product name: Photographic paper Krispia (high gloss), manufactured by Seiko Epson Corporation.
Glossy paper 4:
Product name: Advanced Photo Paper (Glossy), manufactured by Hewlett-Packard Japan.
Glossy paper 5:
Product name: photographic paper (BP71G) manufactured by Brother Co., Ltd.
Plain paper 1:
Product name PB PAPER GF-500 manufactured by Canon Inc.

In the following evaluation tests, a colorimetry system (trade name: SpectroEye ^RTM , manufactured by X-right) was used for measurement of reflection density. Colorimetry was performed under the conditions of DIN as a density standard, a measurement wavelength of 510 nm to 550 nm, a viewing angle of 2 degrees, and a light source D50.

[(C) Print density test]
Of each test piece, the print density was measured by the colorimetric system for the gradation portion having the highest print density. The results are shown in Table 6 below.

  From the results shown in Table 6, the print density of Comparative Example 1 was extremely inferior to that of Example 1 in any glossy paper and plain paper.

[(D) Light resistance test]
Made by Suga Test Instruments Co., Ltd., trade name Low temperature cycle xenon weatherometer-Each test piece is installed in XL75, and irradiated for 168 hours under conditions of irradiance of 100,000 Lux, humidity of 60% RH, and temperature of 24 ° C. went. For the recorded images of each test piece before and after exposure to xenon light, CIE L *, a *, and b * are measured under the above colorimetric conditions, and the color difference ΔE is calculated by the following formula. Evaluated by. Note that the smaller the obtained color difference ΔE, the smaller the color change and the better. The results are shown in Table 7 below.
For the light resistance test, the reflection density was measured for the portion where the reflection density D value of the recorded material before the test was closest to 1.0.

In the following calculation formulas, ΔL *, Δa *, and Δb * mean differences between L *, a *, and b * before and after exposure, respectively.
ΔE = (ΔL * ² + Δa * ² + Δb * ² ) ^1/2

  From the results of Table 7, Comparative Example 1 showed inferior results to Example 1 in light resistance in any glossy paper and plain paper.

[Example 6]
In the same manner as in Example 2 except that 3.7 parts of aniline used in Example 2 is replaced with 4.3 parts of m-toluidine, a red powder of the dye of the present invention represented by the following formula (11) 3. 2 parts (λmax: 535 nm) were obtained.

[Example 7]
After adding 4.5 parts of the pigment | dye represented by Formula (11) obtained in Example 5 to 36.0 parts of 5% fuming sulfuric acid, it reacted at 15-20 degreeC for 3 hours. The obtained solution was added to 100 parts of ice water and then stirred at room temperature for 20 minutes. The solid precipitated from this liquid was collected by filtration and washed with 100 parts of water to obtain 11.7 parts of a wet cake. The obtained wet cake was added to 50 parts of ethanol and 15 parts of water, and stirred at room temperature for 1 hour. This solution was neutralized with 25% aqueous sodium hydroxide solution to pH 7.0-8.0, and the precipitated solid was collected by filtration and dried to obtain an ionic hydrophilic group represented by the following formula (12). This gave 4.9 parts (λmax: 524 nm) of a red powder of the dye of the present invention.

[Example 8]
Example 8 describes another method for synthesizing the dye represented by the formula (12).
(Process 1)
Instead of 105.1 parts of the compound of the formula (8) used in Example 4, 109.6 parts of the compound of the following formula (13) are used in the same manner as in Example 4 (Step 1), 111 parts of the compound represented by (14) were obtained.

(Process 2)
Example 4 (Step 2), except that 4.5 parts of the compound represented by Formula (9) used in Example 4 (Step 2) is replaced with 4.5 parts of the compound represented by Formula (14). In the same manner as above, 5.0 parts of a red powder of the dye of the present invention represented by the formula (12) was obtained.

[Example 9]
(Process 1)
In 30 parts of N, N-dimethylformamide, 4.4 parts of the dye of the formula (4) obtained in Example 1 (Step 1), 4.4 parts of 2-fluoroaniline, copper (II) acetate monohydrate 0.1 part of the product and 1.5 parts of sodium acetate were added and reacted at 115 to 120 ° C. for 8 hours. The reaction solution was cooled to 80 ° C., 100 parts of methanol was added dropwise, the precipitated solid was collected by filtration, and dried to obtain 3.3 parts of a red powder of a compound represented by the following formula (15).

(Process 2)
Example 4 (step 2) except that 4.5 parts of the compound represented by formula (9) used in Example 4 (step 2) is changed to 4.5 parts of the compound represented by formula (15). ), A red powder (λmax: 511 nm) of the dye of the present invention having an ionic hydrophilic group represented by the following formula (16) was obtained.

[Example 10]
(Process 1)
In the same manner as in Example 9 (Step 1), except that 4.4 parts of 2-fluoroaniline used in Example 9 (Step 1) is replaced with 5.1 parts of 2-chloroaniline, the following formula (17) 3.4 parts of a red powder of the compound represented were obtained.

(Process 2)
Example 4 (step 2) except that 4.5 parts of the compound represented by formula (9) used in Example 4 (step 2) is replaced with 4.5 parts of the compound represented by formula (17). In the same manner as above, a red powder (λmax: 515 nm) of the dye of the present invention having an ionic hydrophilic group represented by the following formula (18) was obtained.

[Example 11]
(Process 1)
In the same manner as in Example 8 (Step 1), except that 4.4 parts of 2-fluoroaniline used in Example 9 (Step 1) is replaced with 4.9 parts of 3-methoxyaniline, the following formula (19) 3.3 parts of a red powder of the compound represented were obtained.

(Process 2)
Example 4 (step 2) except that 4.5 parts of the compound represented by formula (9) used in Example 4 (step 2) is replaced with 4.5 parts of the compound represented by formula (19). In the same manner as above, a red powder (λmax: 521 nm) of the dye of the present invention having an ionic hydrophilic group represented by the following formula (20) was obtained.

[Example 12]
(Process 1)
It is represented by the following formula (21) in the same manner as in Example 9 (Step 1) except that 4.4 parts of 2-fluoroaniline in Example 9 (Step 1) is replaced with 6.0 parts of 3-acetamidoaniline. This gave 3.5 parts of red powder of the compound.

(Process 2)
The same procedure as in Example 7 was conducted except that 4.5 parts of the compound represented by formula (9) used in Example 4 (step 2) was replaced with 4.5 parts of the compound represented by formula (21). A red powder (λmax: 525 nm) of the dye of the present invention represented by the following formula (22) and having an ionic hydrophilic group was obtained.

[Example 13]
In 15 parts of N-methyl-2-pyrrolidone, 3.0 parts of the dye represented by the formula (22) obtained in Example 12 (Step 2) and 0.3 part of potassium carbonate were added and heated to 30 ° C. . After 0.5 part of acetyl chloride was added dropwise over 30 minutes, the reaction was carried out for 10 hours. The resulting reaction solution was added to a mixed solution of 100 parts of 25% aqueous sodium chloride solution and 10 parts of 35% hydrochloric acid and stirred at room temperature. The solid precipitated from this liquid was collected by filtration and washed with a 20% aqueous sodium chloride solution to obtain 4.0 g of a wet cake. The obtained wet cake was added to a mixed solution of 25 parts of methanol and 50 parts of 2-propanol and stirred at 60 ° C. for 1 hour, and then the solid was collected by filtration and dried to be expressed by the following formula (23). 2.0 parts (λmax: 519 nm) of a red powder of the dye of the present invention having an ionic hydrophilic group was obtained.

[Example 14]
It has an ionic hydrophilic group represented by the following formula (24) in the same manner as in Example 13 except that 0.5 part of acetyl chloride used in Example 13 is replaced with 1.2 part of p-toluenesulfonyl chloride. 0.8 parts (λmax: 517 nm) of a red powder of the dye of the present invention was obtained. In addition, “Ts” in Formula (24) means a p-toluenesulfonyl group.

[Example 14]
In 20 parts of N, N-dimethylformamide, 3.0 parts of the dye represented by the formula (22) obtained in Example 11 (Step 2) and 1.1 parts of phthalic anhydride are added and heated to 75 ° C. And reacted for 1 hour.
The obtained reaction solution was added to 70 parts of ice water, and 10 parts of sodium chloride was added and stirred. The solid precipitated from this liquid was collected by filtration and washed with a 20% aqueous sodium chloride solution to obtain 8.0 g of a wet cake. The obtained wet cake was added to a mixed solution of 50 parts of methanol and 150 parts of 2-propanol, and stirred at 60 ° C. for 1 hour. 3.0 parts (λmax: 520 nm) of a red powder of the dye of the present invention having an ionic hydrophilic group was obtained.

[Example 15]
It is represented by the following formula (26) in the same manner as in Example 14 except that 1.1 parts of phthalic anhydride used in Example 14 is replaced with 1.6 parts of 2,3-naphthalenedicarboxylic anhydride. 3.0 parts (λmax: 523 nm) of red powder of the dye of the present invention having an ionic hydrophilic group was obtained.

  Each dye of the present invention obtained in each of the above examples showed excellent printing density and light resistance, similar to the dye obtained in Example 3.

[Synthesis example]
The compound of formula (13) used in Example 8 (Step 1) was synthesized as follows.
In 30 parts of N, N-dimethylformamide, 3.2 parts of the compound of the above formula (3) (can be purchased as a commercial product), 0.4 part of m-toluidine, copper (II) acetate monohydrate 0.1 And 1.5 parts of sodium acetate were added and reacted at 115-120 ° C. for 8 hours. After cooling the reaction solution to 80 ° C., 100 parts of methanol was added dropwise to the solution, and the precipitated solid was collected by filtration. The obtained solid was dried to obtain 2.4 parts of a blue powder of the compound of the formula (13).

  The image recorded by the dye represented by the formula (1) of the present invention and the ink composition containing the dye is extremely excellent in printing density and light resistance, and thus is very useful for various uses, particularly for inkjet recording. is there.

Claims (18)

The pigment | dye represented by following formula (1), its salt, or mixtures thereof.

(In formula (1), n represents an integer of 0 to 5, and R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a substituent.) R ¹ , R ² , R ³ and R ⁴ in the formula (1) are each independently selected from a hydrogen atom; an alkyl group; an arylalkyl group; a nitrogen atom, an oxygen atom and a sulfur atom as ring-constituting atoms. A 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms; a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring-constituting atoms 5-ring or 6-membered heterocyclic amino group condensed with one benzene ring on the ring group; alkoxy group; aryloxy group; alkylcarbonylamino group; carbamoyl group; hydroxy group; alkylsulfonyl group; arylthio group The dye or a salt thereof, or a mixture thereof according to claim 1, which is a group selected from the group consisting of: a cyano group; an amino group; an arylamino group; a halogen atom;
However, the dye represented by the formula (1) or a salt thereof, or a mixture thereof may further have an ionic hydrophilic group as a substituent. The dye or a salt thereof, or a mixture thereof according to claim 1 or 2, wherein R ⁴ in the formula (1) is a halogen atom or an arylamino group which may have a substituent. R ⁴ in the formula (1) is a halogen atom, or an arylamino group having at least one ionic hydrophilic group as a substituent, or a dye or a salt thereof according to claim 1 or their blend. In the formula (1), n is 0, R ¹ is an alkyl group, R ² and R ³ are hydrogen atoms, and R ⁴ is at least one ionicity as a halogen atom or a substituent. The dye or a salt thereof, or a mixture thereof according to claim 1, which is an arylamino group having a hydrophilic group. An ink composition comprising the dye represented by the formula (1) according to any one of claims 1 to 5 or a salt thereof, or a mixture thereof, and water. The ink composition according to claim 6, further comprising a water-soluble organic solvent. The content of the inorganic impurities contained in the total mass of the pigment represented by the formula (1) or a salt thereof, or a mixture thereof is 1 with respect to the total mass of the pigment, a salt thereof, or a mixture thereof. The ink composition according to claim 6 or 7, wherein the ink composition is not more than mass%. The content of the coloring matter represented by the formula (1) or a salt thereof, or a mixture thereof is 0.1 to 20% by mass with respect to the total mass of the ink composition. The ink composition described in 1. The ink composition according to any one of claims 6 to 9, which is used for inkjet recording. An ink jet recording method for performing recording by ejecting droplets of the ink composition according to claim 10 in accordance with a recording signal and attaching the droplets to a recording material. The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. The inkjet recording method according to claim 12, wherein the information transmission sheet is plain paper or a sheet having an ink receiving layer containing a porous white inorganic substance. A colored body colored with the pigment according to any one of claims 1 to 5, a salt thereof, or a mixture thereof. A colored body colored with the ink composition according to any one of claims 6 to 10. A colored body colored by the ink jet recording method according to claim 11. An inkjet printer loaded with a container containing the ink composition according to claim 10. The compound represented by the following formula (103) is heated in a fuming sulfuric acid at a temperature of 80 ° C. or higher to produce the dye represented by the formula (1) according to claim 1 or a salt thereof, or a mixture thereof. how to.

(In formula (103), n, R ¹ , R ² , R ³ , and R ⁴ all represent the same meaning as in formula (1) according to claim 1).