JP2005111699A - Inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording method having little bleeding of an image even under a high humidity condition as well as having high weatherability. <P>SOLUTION: In the inkjet recording method in which ink drops are ejected on the inkjet sheet having an ink receiving layer on a support to form an image by printing according to image information, at least one ink and a betaine compound are contained in the ink receiving layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ink jet recording using a liquid ink such as a water-based ink (using a dye or pigment as a coloring material) and an oil-based ink, or a solid ink which is solid at room temperature and melted and liquefied for printing. In particular, the present invention relates to an ink jet recording method excellent in image weather resistance and image durability under high humidity conditions.

In recent years, with the rapid development of the information technology industry, various information processing systems have been developed, and recording methods and recording apparatuses suitable for the information processing systems have been developed and put into practical use.
Among these recording methods, the inkjet recording method is capable of recording on a variety of recording materials, has advantages such as being relatively inexpensive and compact in hardware (device), and excellent in quietness. It has also been widely used for so-called home use.

In addition, with the recent increase in resolution of inkjet printers, it has become possible to obtain so-called photographic-like high-quality recorded matter. With the progress of such hardware (devices), recording for inkjet recording has become possible. Various seats have been developed.
The characteristics required for this recording sheet for ink jet recording are generally (1) fast drying (high ink absorption speed), and (2) ink dot diameter is appropriate and uniform. (No blurring), (3) good graininess, (4) high dot roundness, (5) high color density, (6) high chroma (dullness) (7) The water resistance, light resistance, and ozone resistance of the print portion are good, (8) the whiteness of the recording sheet is high, and (9) the storage stability of the recording sheet is good ( Does not cause yellowing coloring even after long-term storage, does not blur images after long-term storage (good aging blur), and (10) is difficult to deform and has good dimensional stability (curl is sufficiently small) (11) Good hard running performance, etc. That.
Furthermore, in the use of photo glossy paper used for the purpose of obtaining so-called photographic-like high-quality recorded matter, in addition to the above properties, gloss, surface smoothness, photographic paper-like texture similar to silver salt photography, etc. Is also required.

  In recent years, an ink jet recording sheet having a porous structure in an ink receiving layer has been developed and put into practical use for the purpose of improving the various properties described above. Such an ink jet recording sheet has a porous structure, and thus has excellent ink receptivity (fast drying property) and high gloss.

For example, in Japanese Patent Application Laid-Open Nos. 10-119423 and 10-217601, etc., for inkjet recording, which includes fine inorganic pigment particles and a water-soluble resin, and an ink receiving layer having a high porosity is provided on a support. A sheet has been proposed.
These recording sheets, particularly ink jet recording sheets provided with an ink receiving layer having a porous structure using silica as inorganic pigment fine particles, are excellent in ink absorptivity and can form high resolution images. It has high ink receiving performance and can exhibit high gloss.

  As the ink for ink jet, water-based ink, oil-based ink, or solid (melted type) ink is used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

  The colorants used in these inkjet inks have high solubility in solvents, high density recording, good hue, fastness to light, heat, air, water and chemicals. It is required to be excellent in fixability, good fixability to the image receiving material and difficult to bleed, excellent storability as ink, non-toxicity, high purity, and available at low cost. Has been. However, it is extremely difficult to search for colorants that meet these requirements at a high level. Various dyes and pigments have already been proposed and actually used for inkjet, but no colorant that satisfies all the requirements has yet been discovered. Conventionally well-known dyes and pigments having a color index (CI) number are difficult to achieve both hue and fastness required for ink jet recording inks. So far, we have been studying dyes that have good hues and are robust, and have developed excellent colorants for inkjet. However, a compound called a water-soluble dye is always substituted with a water-soluble group. It has been found that when the number of water-soluble groups is increased in order to improve the stability of the ink, the formed image tends to bleed under high humidity conditions.

  The inventors have found that it is effective to use a betaine compound to solve the problem caused by bleeding.

In addition, betaine compounds have been found to have the effect of improving the ozone weather resistance and light fastness of dyes, but it has been found that this effect is not sufficient by adding betaine alone to the ink. It was.
JP 10-119423 A Japanese Patent Laid-Open No. 10-217601

  SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording method having little image blur even under high humidity conditions and having excellent weather resistance.

The above object has been achieved by the following means.
1) In an ink jet recording method for forming an image by ejecting ink droplets according to image information onto an ink jet recording material having an ink receiving layer on a support, and forming the image. An ink jet recording method, wherein the layer contains a betaine compound.
2) The inkjet recording method according to item 1, wherein the oxidation potential of at least one dye contained in the ink is 1.0 V or more.
3) The ink jet recording method described in item 1 or 2, wherein the ink receiving layer further contains a water-soluble resin.
4) The water-soluble resin is at least one of a polyvinyl alcohol resin, a cellulose resin, a resin having an ether bond, a resin having a carbamoyl group, a resin having a carboxyl group, and gelatin. The inkjet recording method in any one of -3.
5) The ink jet recording method according to any one of Items 1 to 4, wherein the ink receiving layer further contains fine particles.
6) The inkjet recording method according to any one of Items 1 to 4, wherein the fine particles are at least one of silica fine particles, colloidal silica, alumina fine particles, and pseudoboehmite.
7) The ink jet recording method according to any one of items 1 to 6, wherein the ink receiving layer contains a crosslinking agent capable of crosslinking the water-soluble resin.
8) The ink jet recording method according to any one of 1 to 7, wherein the ink receiving layer further contains a mordant.
9) The ink jet recording method according to any one of items 1 to 8, wherein at least one dye represented by the following general formulas (1) to (4) is used as the dye of the ink.
General formula (1);
(A ₁₁ −N = N−B ₁₁ ) n ₁ -Ly
In the general formula (1), A ¹¹ and B ¹¹ each independently represents an optionally substituted heterocyclic group. n ₁ is 1 or 2, and Ly represents a hydrogen atom, a monovalent substituent, a simple bond, or a divalent linking group. However, when n ₁ is 1, Ly represents a hydrogen atom or a monovalent substituent, and both A ₁₁ and B ₁₁ are monovalent heterocyclic groups. When n ₁ is 2, Ly represents a simple bond or a divalent linking group, one of A ₁₁ and B ₁₁ is a monovalent heterocyclic group, and the other is a divalent heterocyclic group.
General formula (2);

In the general formula (2), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are each independently —SO—Z ₂ , —SO ₂ —Z ₂ , —SO ₂ NR ₂₁ R ₂₂ , sulfo group, —CONR ₂₁ R ₂₂ or —COOR ₂₁ is represented. Z ₂ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted heterocyclic group. R ₂₁ and R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ each independently represent a monovalent substituent.
_{a 21 ~a 24, b 21 ~b} 24 each represent the number of substituents of X ₂₁ to X ₂₄ and Y ₂₁ to Y _24. a _{21 to} a ₂₄ each independently represents a number of 0 to 4, but they are not all 0 at the same time. b ₂₁ ~b ₂₄ represents the number of independently 0-4. Incidentally, when a ₂₁ ~a ₂₄ and b ₂₁ ~b ₂₄ represents the number of 2 or more, plural X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ may be the same as or different from each other to each other.
M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.
General formula (3);

In general formula (3), A represents a 5-membered heterocyclic ring.
B ₃₁ and B ₃₂ are each, = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - or represents a -CR ₃₂ =.
R ₃₅ and R ₃₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group Each group may further have a substituent.
G, R ₃₁ and R ₃₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, complex Ring oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino group) A heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or Aryl It represents a thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group, and each group may be further substituted.
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- or 6-membered ring.
General formula (4);
A ^41- (N = N- (B ⁴¹ ) m) n-N = N-C ⁴¹
In the general formula (4), A ₄₁ , B ₄₁ and C ₄₁ each independently represents an optionally substituted aromatic group or heterocyclic group. m is 1 or 2, and n is an integer of 0 or more.

  According to the ink jet recording method of the present invention, an ink jet recorded image with little image bleeding even under high humidity conditions and excellent weather resistance can be provided. In the present invention, it is considered that weather resistance is improved and bleeding is improved by changing the mordanting state of the dye by the betaine compound.

Hereinafter, the present invention will be described in detail.
The ink-jet ink and recording material of the present invention are characterized by having a betaine compound. However, among the betaine compounds, a betaine surfactant having an oil-soluble group is particularly preferable.
The betaine compound preferably used in the present invention is preferably a betaine-type surfactant having surface activity.

The betaine compound here refers to a compound having both a cationic site and an anionic site in the molecule. Examples of the cationic site include an aminic nitrogen atom, a nitrogen atom of a heteroaromatic ring, a boron atom having four bonds with carbon, and a phosphorus atom. Of these, an amine nitrogen atom or a nitrogen atom of a heteroaromatic ring is preferred. Among them, a quaternary nitrogen atom is particularly preferable. Examples of the anionic site include a hydroxyl group, a thio group, a sulfonamide group, a sulfo group, a carboxyl group, an imide group, a phosphoric acid group, and a phosphonic acid group. Among these, a carboxyl group and a sulfo group are particularly preferable. The charge of the betaine compound (preferably surfactant) molecule as a whole may be a cation, an anion, or neutral, but is preferably neutral.
As the betaine compound used in the present invention, a compound represented by the following general formula (B1) or (B2) is particularly preferably used.
General formula (B1)

In the formula, R _{1 to} R ₃ are alkyl groups (which may be substituted. Preferably they are groups having 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, Dodecyl group, cetyl group, stearyl group, oleyl group, etc.), aryl group (which may be substituted, preferably a group having 6 to 20 carbon atoms. For example, phenyl group, tolyl group, xylyl group, naphthyl group, cumyl group) Group, dodecylphenyl group, etc.) or heterocyclic group (which may be substituted, preferably a group having 2 to 20 carbon atoms, such as pyridyl group, quinolyl group, etc.), An annular structure may be formed. Among these, an alkyl group is particularly preferable. L represents a divalent linking group. As this example, a divalent linking group containing an alkylene group or an arylene group as a basic structural unit is preferable. You may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom, in a connection main chain part. Various substituents can be substituted for R _{1 to} R ₃ or L. For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n -Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms). , For example, propargyl, 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon number) To 20 and particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), amino groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, Particularly preferably, it has 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino and the like, and an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably carbon. 1 to 12, particularly preferably 1 to 8 carbon atoms such as methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy.), Acyl groups (preferably Or a carbon number of 1 to 16, more preferably a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 12, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably carbon 2 to 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 20 carbon atoms). , More preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 16 and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy. An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino A group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), a sulfonylamino group (preferably having a carbon number) 1-20, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably 0-20 carbon atoms, More preferably, it has 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms. Moyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to carbon atoms). For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, methylthio, ethylthio, etc.), arylthio groups (preferably having 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms, such as phenylthio). ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably charcoal) 1 to 16, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably C1-C12, for example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably C1-C20, more preferably C1-C16, particularly preferably C1-C12 Yes, for example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, For example, diethyl phosphoric acid amide, phenyl phosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine source) Child, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms) Preferably, it has 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxa Examples include zolyl, benzimidazolyl, benzothiazolyl, carbazolyl, azepinyl and the like. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring. A plurality of betaine structures may be contained via R _{1 to} R ₃ or L.

In the betaine compound used in the present invention, at least one of R _{1 to} R ₃ or L contains a group having 8 or more carbon atoms. Of these, those containing a long-chain alkyl group in R _{1 to} R ₃ are particularly preferred.

Formula _{^{(B2) (R k) p}} -N- [L m - (COOM n) q] r

  In the formula, R is an alkyl group (which may be substituted. Preferably, it is a group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, cetyl group. Group, stearyl group, oleyl group, etc.), aryl group (which may be substituted, preferably a group having 6 to 20 carbon atoms, for example, phenyl group, tolyl group, xylyl group, naphthyl group, cumyl group, dodecylphenyl). Group), a heterocyclic group (which may be substituted, preferably a group having 2 to 20 carbon atoms, such as a pyridyl group, a quinolyl group, etc.), which are linked to each other to form a cyclic structure. Also good. Among these, an alkyl group is particularly preferable.

  L represents a divalent or higher valent linking group. As this example, a divalent or higher valent linking group containing an alkylene group, an arylene group or the like as a basic structural unit is preferable. You may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom, in a connection main chain part.

  Various substituents can be substituted for R or L. For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n -Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms). , For example, propargyl, 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon number) To 20 and particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), amino groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, Particularly preferably, it has 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino and the like, and an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably carbon. 1 to 12, particularly preferably 1 to 8 carbon atoms such as methoxy, ethoxy, butoxy, etc.), an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy.), Acyl groups (preferably Or a carbon number of 1 to 16, more preferably a carbon number of 1 to 16, particularly preferably a carbon number of 1 to 12, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably carbon 2 to 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 20 carbon atoms). , More preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl, etc.), an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 2 carbon atoms). 16 and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy. An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino A group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), a sulfonylamino group (preferably having a carbon number) 1-20, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably 0-20 carbon atoms, More preferably, it has 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms. Moyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to carbon atoms). For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, methylthio, ethylthio, etc.), arylthio groups (preferably having 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms, such as phenylthio). ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably charcoal) 1 to 16, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably C1-C12, for example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably C1-C20, more preferably C1-C16, particularly preferably C1-C12 Yes, for example, ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, For example, diethyl phosphate amide, phenyl phosphate amide, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine Child, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms) Preferably it has 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzox Examples include zolyl, benzimidazolyl, benzothiazolyl, carbazolyl, azepinyl and the like. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring. A plurality of betaine structures may be contained via R or L.

  M represents a hydrogen atom, an alkali metal cation (for example, sodium ion, potassium ion, lithium ion, cesium ion), an ammonium ion, or an aminic organic cation (in the case of primary to tertiary amines, protonated ones, for example, protons). Methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, diazabicycloundecene, diazabicyclooctane, piperidine, pyrrolidine, morpholine, N-methylpiperidine, N-methylmorpholine, pyridine, pyrazine, aniline, N, N-dimethylaniline, etc. In the case of a quaternary ammonium salt, for example, tetramethylammonium ion, tetraethylmonium ion, trimethylbenzylammonium ion, methylpyridinium ion, benzil Pyridinium ion.) Represents the. Among them, a temporary metal ion or a hydrogen atom is particularly preferable.

q represents an integer of 1 or more, and r represents an integer of 1 to 4. k represents an integer of 0 or more and 4 or less, and m represents an integer of 1 or more. p represents an integer of 0 or more and 4 or less, and p + r is 3 or 4. When p + r is 4, the N atom becomes a protonated ammonium atom (= N ⁺ =). When m is 2 or more, L may be the same or different. When q is 2 or more, the COOMs may be the same or different. When r is 2 or more, L ^m- (COOM) _q may be the same or different. When k is 2 or more, R may be the same or different. When p is 2 or more, R ^k may be the same or different.

  Furthermore, it is preferable that R or L contains a hydrocarbon group having 8 or more carbon atoms, and a compound represented by the following general formula (B3) is most preferably used.

General formula (B3) RN- (L-COOM ¹ ) ₂

In the formula, R, L, q, r, m and p have the same meaning as in the general formula (2). M ¹ is an alkali metal ion or a hydrogen atom. However, p + r is 3. When p is 2 or more, R may be the same or different.

  Preferred examples of the compound of the present invention are enumerated below, but the present invention is of course not limited thereto.

  The preferred addition amount of the betaine-based surfactant has a wide range, but when added to the ink, it is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass in the ink.

In the present invention, a betaine compound is also added to the recording material. The preferred amount of the betaine compound in the recording material (preferably betaine surfactant) is a wide range, preferably from 0.001 to 100 g / m ^2, more preferably at 0.01 to 10 g / m ^2.

  The betaine compound added to the ink and the betaine compound added to the recording material may be the same or different.

  Further, the total mass of inorganic ions contained in the betaine surfactant is preferably suppressed to 5% by mass or less with respect to betaine. The inorganic ions here are inorganic ions of counter ions of dyes, inorganic ions derived from inorganic salts that are impurities contained in betaine surfactants, and inorganic ions that become counter ions of ion components that deviate from the ion equivalent of betaine compounds. Represents the sum of inorganic ions introduced from inorganic salts used for pH adjustment, inorganic ions introduced from ink additives such as chelating agents and preservatives. However, in the present invention, ammonium ions are treated as volatile compounds and excluded from these inorganic ions.

Various techniques can be used to reduce the content of inorganic ions in the ink as much as possible.
First, a method of removing inorganic ions contained in a material used for ink at the time of material synthesis can be mentioned. In the case of a water-soluble ink material, many ion dissociable groups are often introduced particularly for the purpose of improving water solubility. At this time, a large amount of an inorganic substance is included at the time of material synthesis, or an inorganic ion is necessarily included as a counter ion. In order to remove the former ions, a desalting purification method by electrolysis dialysis using an ion-selective permeable membrane, a method using an ion exchange resin, a desalting purification by a gel filtration method, and the like can be performed.
In addition, a method of positively exchanging ions during synthesis can be used. For example, a method of exchanging with metal ions by adding excess ammonia or organic amines, or a method of exchanging with organic carboxylic acids in the case of anions can be mentioned.

Second, the desalting and purification may be performed in a state of ink raw material, that is, a concentrated aqueous solution (pre-ink) in which various materials are dissolved in a solvent such as water. In some cases, desalting and purification with a finished ink is also possible.
The ink used in the ink set of the present invention is an ink obtained by dissolving or dispersing a dye in water and a water-soluble organic solvent. Of these, aqueous inks using water-soluble dyes are preferred. In the ink set, the ink having a betaine compound may have any color, and an ink having no color may be prepared for the betaine compound.

When the betaine compound of the present invention is used, bubbles may be generated in the ink. Since the bubbles may cause a printing defect in ink jet recording, this problem can be solved by adding a compound (= antifoaming agent) having an action of eliminating bubbles to the ink.
As an antifoaming agent, various things, such as a pluronic type antifoaming agent (polyoxyethylene-polyoxypropylene type antifoaming agent) and a silicone type antifoaming agent, can be used.

Next, the dyes used in the present invention including the dyes represented by the general formulas (1) to (4) will be described.
In the present invention, it is preferable to use a dye having an oxidation potential nobler than 1.0V (preferably a dye nobler than 1.1V, particularly preferably a dye nobler than 1.2V). By making it nobler than 1.0 V, an image excellent in image durability, particularly ozone resistance can be obtained.

  A person skilled in the art can easily measure the value of the oxidation potential (Eox). Regarding this method, see, for example, P.I. Delahay, "New Instrumental Methods in Electrochemistry" (published by Interscience Publishers, 1954). J. et al. "Electrochemical Methods" by Bard et al. (Published by John Wiley & Sons, 1980), "Electrochemical Measurement Method" by Akira Fujishima et al. (Published by Gihodo Publishing Co., Ltd., 1984), and the like.

Specifically, the oxidation potential is 1 × 10 ⁻⁴ to 1 × 10 ^{−6 in} a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. It is dissolved at a concentration of mol / liter and measured as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography. Although this value may be deviated by several tens of mil volts due to the influence of the liquid potential difference or the liquid resistance of the sample solution, the reproducibility of the potential can be ensured by inserting a standard sample (for example, hydroquinone). In order to uniquely define the potential, in the present invention, a direct current polarizer is used in dimethylformamide containing 0.1 moldm ⁻³ tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye is 0.001 moldm ⁻³ ). The value (vs SCE) measured by ography is taken as the oxidation potential of the dye. In the case of a water-soluble dye, it may be difficult to dissolve directly in N, N-dimethylformamide. In that case, after dissolving the dye with as little water as possible, the water content should be 2% or less. Dilute with N, N-dimethylformamide and measure.

  The value of the oxidation potential (Eox) represents the ease of electron transfer from the sample to the electrode, and the larger the value (the oxidation potential is noble), the more difficult the electron transfer from the sample to the electrode, in other words, less oxidation. Represents that. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing an electron withdrawing group, and the oxidation potential becomes lower by introducing an electron donating group.

  Examples of the dye having the above characteristics include azo dyes (yellow dye, magenta dye, black dye) and phthalocyanine dye (cyan dye) having specific performance and structure. Hereinafter, each dye will be described.

[Yellow dye]
The yellow dye used in the present invention measures the reflection density through a status A filter after printing the ink containing the yellow dye on a reflective medium, and the reflection density (D _B ) in the yellow region is 0.90 to 0.90. 1. The dot of 1.10 is defined as the initial density of the ink, and this print is forcibly faded using an ozone fading tester capable of always generating 5 ppm of ozone, and the reflection density is the initial density. When the forced fading rate constant (k) obtained from the time (t) until 80% (residual rate) is reached, the rate constant is set to 5.0 × 10 ⁻² [hour ⁻¹ ] or less. Those are preferred. Thereby, fastness, especially fastness to ozone gas can be improved. From this viewpoint, the rate constant is preferably 3.0 × 10 ⁻² [hour ⁻¹ ] or less, and 1.0 × 10 ⁻² [ hour ^-1 ] or less is more preferable.
Here, the reflection density is a value measured by a status A filter (blue) using a reflection densitometer (X-Rite 310TR). The forced fading rate constant (k) is a value obtained from the remaining rate = exp (−kt), that is, k = (− ln 0.8) / t.

  Further, as described above, the yellow dye preferably has an oxidation potential nobler than 1.0 V (vs SCE), more preferably nobler than 1.1 V (vs SCE), and 1.2 V ( It is particularly preferred that it is noble than (vs SCE). In the present invention, it is desirable to introduce an electron withdrawing group into the yellow dye skeleton to make the oxidation potential more noble.

  In addition, the dye used in the present invention preferably has good fastness and good hue, and in particular, the absorption spectrum has a good tail on the long wave side. Therefore, a yellow dye having an λmax of 390 nm to 470 nm in an aqueous solution and a ratio I (λmax + 70 nm) / I (λmax) of the absorbance I (λmax) of λmax to the absorbance I (λmax + 70 nm) of λmax + 70 nm Is preferable, and 0.1 or less is more preferable. The lower limit of the ratio is ideally 0, but is practically about 0.01.

  Examples of the dye satisfying such oxidation potential and absorption characteristics include dyes represented by the general formula (1).

Formula _{(1) :( A 11 -N =} N-B 11) n 1 -Ly

In the general formula (1), A ₁₁ and B ₁₁ each independently represents an optionally substituted heterocyclic group. The heterocyclic ring is preferably a heterocyclic ring composed of a 5-membered ring or a 6-membered ring, and may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. It may be a ring or a non-aromatic heterocyclic ring. As the hetero atom constituting the heterocyclic ring, N, O and S atoms are preferable.
n ₁ represents an integer selected from 1 or 2, and 2 is more preferable. Ly represents a hydrogen atom, a monovalent substituent, a simple bond, or a divalent linking group. However, when n ₁ is 1, Ly represents a hydrogen atom or a monovalent substituent, and both A ₁₁ and B ₁₁ are monovalent heterocyclic groups. When n ₁ is 2, Ly represents a simple bond or a divalent linking group, one of A ₁₁ and B ₁₁ is a monovalent heterocyclic group, and the other is a divalent heterocyclic group.

In the general formula (1), as the heterocycle represented by A ₁₁ , 5-pyrazolone, pyrazole, triazole, oxazolone, isoxazolone, barbituric acid, pyridone, pyridine, rhodanine, pyrazolidinedione, pyrazolopyridone, meldrum acid In addition, a condensed heterocyclic ring obtained by further condensing a hydrocarbon aromatic ring or a heterocyclic ring to these heterocyclic rings is preferable. Of these, 5-pyrazolone, 5-aminopyrazole, pyridone, 2,6-diaminopyridine and pyrazoloazoles are preferable, and 5-aminopyrazole, 2-hydroxy-6-pyridone and pyrazolotriazole are particularly preferable.

Examples of the heterocyclic ring represented by B ₁₁ include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, Examples include benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Of these, pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, and benzoisoxazole are preferable, and quinoline, thiophene , Pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, thiadiazole are more preferable, and pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole Is particularly preferred.

The heterocyclic group represented by A ₁₁ and B ₁₁ may be substituted, and examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. , Cyano group, hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonyl Amino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfur group Ynyl, alkyl and arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, silyl, or The following ionic hydrophilic groups are mentioned as examples.

Examples of the monovalent substituent represented by Ly include a substituent that may be substituted on the heterocyclic group represented by A ₁₁ and B ₁₁ , and the following ionic hydrophilic group.
Examples of the divalent linking group represented by Ly include an alkylene group, an arylene group, a heterocyclic residue, -CO-, -SOn- (n is 0, 1, 2), -NR- (R is a hydrogen atom, an alkyl group). , Represents an aryl group), —O—, and a divalent group obtained by combining these linking groups, and further they may be substituted with the heterocyclic group represented by A ₁₁ and B ₁₁ above. Or you may have the following ionic hydrophilic group.

  When the dye of the general formula (1) is used as a water-soluble dye, it preferably has at least one ionic hydrophilic group in the molecule. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a carboxyl group. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable.

Among the dyes represented by the general formula (1), the portion represented by A ₁₁ —N═N—B _{11 corresponds} to the following general formula (1-A), (1-B) or (1-C) Dyes are preferred.
Formula (1-A)

  In general formula (1-A), R1 and R3 represent a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group or an ionic hydrophilic group, R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a carbamoyl group, an acyl group, an aryl group or a heterocyclic group, and R4 represents a heterocyclic group.

  Formula (1-B)

  In general formula (1-B), R5 represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group, and Za is -N =, -NH-, or -C (R11) =, Zb and Zc each independently represent -N = or -C (R11) =, and R11 represents a hydrogen atom or a nonmetallic substituent. R6 represents a heterocyclic group.

  Formula (1-C)

  In general formula (1-C), R7 and R9 are each independently a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group. Or R8 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, an acylamino group, a sulfonylamino group, an alkoxycarbonylamino group, a ureido group, an alkylthio Represents a group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, an alkylamino group, an arylamino group, a hydroxy group, or an ionic hydrophilic group, and R10 represents a heterocyclic group.

  In the general formulas (1-A), (1-B), and (1-C), the alkyl group represented by R1, R2, R3, R5, R7, R8, and R9 includes an alkyl group having a substituent and none. Substituted alkyl groups are included. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Examples of the substituent include a hydroxy group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and 4-sulfobutyl.

The cycloalkyl group represented by R1, R2, R3, R5, R7, R8 and R9 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include cyclohexyl.
The aralkyl group represented by R1, R2, R3, R5, R7, R8 and R9 includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include benzyl and 2-phenethyl.

  The aryl group represented by R1, R2, R3, R5, R7, R8 and R9 includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 20 carbon atoms. Examples of the substituent include a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an alkylamino group, an acylamino group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl.

  The alkylthio group represented by R1, R2, R3, R5, R7, R8 and R9 includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include methylthio and ethylthio.

  The arylthio group represented by R1, R2, R3, R5, R7, R8 and R9 includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the arylthio group include a phenylthio group and p-tolylthio.

  The heterocyclic group represented by R2 is preferably a 5- or 6-membered heterocyclic ring, which may be further condensed. As the hetero atom constituting the heterocyclic ring, N, S, and O are preferable. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic ring may be further substituted, and examples of the substituent include the same substituents as the aryl group described above. Preferred heterocycles are 6-membered nitrogen-containing aromatic heterocycles, and triazine, pyrimidine, and phthalazine can be given as preferred examples.

Examples of the halogen atom represented by R8 include a fluorine atom, a chlorine atom, and a bromine atom.
The alkoxy group represented by R1, R3, R5, and R8 includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the substituent include a hydroxy group and an ionic hydrophilic group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R8 includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the aryloxy group include phenoxy, p-methoxyphenoxy and o-methoxyphenoxy.
The acylamino group represented by R8 includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include the same substituents as the aryl group described above. Examples of the acylamino group include acetamide, propionamide, benzamide and 3,5-disulfobenzamide.

The sulfonylamino group represented by R8 includes an alkylsulfonylamino group, an arylsulfonylamino group, and a heterocyclic sulfonylamino group, and each alkyl group part, aryl group part, and heterocyclic part may have a substituent. Good. Examples of the substituent include the same substituents as the aryl group described above. The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms. Examples of the sulfonylamino group include methylsulfonylamino and ethylsulfonylamino.
The alkoxycarbonylamino group represented by R8 includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include ethoxycarbonylamino.

The ureido group represented by R8 includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include 3-methylureido, 3,3-dimethylureido, and 3-phenylureido.
The alkoxycarbonyl group represented by R7, R8 and R9 includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The carbamoyl group represented by R2, R7, R8 and R9 includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
The sulfamoyl group having a substituent represented by R8 and the unsubstituted sulfamoyl group are included. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

The sulfonyl group represented by R8 includes an alkylsulfonyl group, an arylsulfonyl group or a heterocyclic sulfonyl group, which may further have a substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonyl group include methylsulfonyl and phenylsulfonyl.
The acyl group represented by R2 and R8 includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include acetyl and benzoyl.

  The amino group represented by R8 includes an amino group having a substituent and an unsubstituted amino group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group. Examples of the amino group include methylamino, diethylamino, anilino and 2-chloroanilino.

  The heterocyclic group represented by R4, R6 and R10 is the same as the optionally substituted heterocyclic group represented by B in the general formula (1), and preferred examples, more preferred examples, and particularly preferred examples are also included. Same as above. Examples of the substituent include an ionic hydrophilic group, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkyl or arylthio group, a halogen atom, a cyano group, a sulfamoyl group, a sulfoneamino group, a carbamoyl group, and an acylamino group. And the alkyl group and aryl group may further have a substituent.

  In the general formula (1-B), Za represents —N═, —NH—, or —C (R11) ═, and Zb and Zc each independently represent —N═ or —C (R11) ═. R11 represents a hydrogen atom or a nonmetallic substituent. As the nonmetallic substituent represented by R11, a cyano group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, or an ionic hydrophilic group is preferable. Each of the substituents is synonymous with each substituent represented by R 1, and preferred examples are also the same. Examples of the heterocyclic skeleton composed of two 5-membered rings included in the general formula (1-B) are shown below.

Examples of the substituent when each of the substituents described above may further have a substituent include the heterocyclic groups represented by the heterocyclic rings A ₁₁ and B ₁₁ in the general formula (1) described above. The substituent which may be substituted can be mentioned.

Among the above general formulas (1-A) to (1-C), preferred is the general formula (1-A), and among them, those represented by the following general formula (1-A1) are particularly preferred.
Formula (1-A1)

In General Formula (1-A1), R ²¹ and R ²³ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, or an aryl group. R ²² represents a hydrogen atom, an aryl group or a heterocyclic group. X and Y, one represents a nitrogen atom and the other represents -CR ^24. R ²⁴ is hydrogen atom, halogen atom, cyano group, alkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkyloxycarbonyl group, carbamoyl group, alkoxy group, aryl group, arylthio group, arylsulfonyl group, arylsulfinyl. Represents a group, an aryloxy group or an acylamino group. Of these, a hydrogen atom, an alkyl group, an alkyl and arylthio group, and an aryl group are preferable, and a hydrogen atom, an alkylthio group, and an aryl group are particularly preferable. Each substituent may be further substituted.

  Preferred dyes used in the present invention include those described in Japanese Patent Application Nos. 2003-286844, 2002-211683, 2002-124832, 2003-128953, and 2003-41160. Among them, the compounds exemplified below are particularly preferable. In addition, the dye which can be used for this invention is not limited to these. These compounds can be synthesized with reference to JP-A-2-24191 and JP-A-2001-279145 in addition to the above patents.

  The content of the yellow dye represented by the general formula (1) in the ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

[Cyan dye]
Next, the phthalocyanine dye that is a cyan dye will be described in detail.
It is preferable that the phthalocyanine dye used in the present invention is excellent in both light resistance and ozone resistance and has a small change in hue and surface state (bronzing is difficult to occur and dye is difficult to precipitate).

  As for light resistance, xenon light (Xe 1.1 W / m (intermittent condition)) was irradiated for 3 days with a TAC filter on the part where the reflection density OD of the image printed on the Epson PM photographic image receiving paper was 1.0. It is preferable that the dye residual ratio (reflection density after irradiation / initial density × 100) is 90% or more. Moreover, it is preferable that the dye residual rate at the time of 14 days is 85% or more.

Regarding the change in hue and surface state, the amount of Cu ions present as phthalate due to decomposition of the phthalocyanine dye serves as an index. It is preferable that the equivalent amount of Cu ions present in the actual print is 10 mg / m ² or less. The amount of Cu ions flowing out of the print is formed as a solid image with a Cu ion conversion amount of 20 mg / m ² or less. After this image is stored in a 5 ppm ozone environment for 24 hours and then faded by ozone, it flows out of the image into the water. The amount of Cu ions is preferably 20% or less. Before the fading, all Cu compounds are trapped in the recording material.

  The phthalocyanine dye having the physical properties as described above 1) increases the oxidation potential, 2) increases the association property, 3) introduces an association promoting group, and strengthens the hydrogen bond during π-π stacking. 4) It is obtained by not inserting a substitution machine at the α-position, that is, by making stacking easy.

The structural characteristics of the phthalocyanine dyes used in the present invention are the phthalocyanine dyes used in conventional inks derived from sulfonation of unsubstituted phthalocyanines, so the number and position of substituents are specified. Whereas the mixture cannot be used, a phthalocyanine dye capable of specifying the number and position of substituents is used. The first structural feature is that the phthalocyanine dye does not go through sulfonation of unsubstituted phthalocyanine. The second structural feature is that it has an electron-withdrawing group at the β-position of the benzene ring of phthalocyanine, and particularly preferably has an electron-withdrawing group at the β-position of all benzene rings. Specifically, those in which a sulfonyl group is substituted (Japanese Patent Application Nos. 2001-47013 and 2001-190214), and those in which all sulfamoyl groups are substituted (Japanese Patent Application Nos. 2001-24352 and 2001-2001).
189982), a heterocyclic sulfamoyl group substituted (Japanese Patent Application No. 2001-96610, Japanese Patent Application No. 2001-190216), a heterocyclic sulfonyl group substituted (Japanese Patent Application No. 2001-76689, Japanese Patent Application No. 2001-190215), a specific sulfamoyl group Are substituted (Japanese Patent Application No. 2001-57063), those substituted with a carbonyl group (Japanese Patent Application No. 2002-012869), those having specific substituents for improving solubility, ink stability, and measures against bronzing. Have an asymmetric carbon (Japanese Patent Application No. 2002-012868) and a Li salt (Japanese Patent Application No. 2002-012864) are useful.

  The first characteristic feature is that it has a high oxidation potential (noble from 1.0 V). The second physical property is a strong associative property. Specific examples include those that define the association of oil-soluble dyes (Japanese Patent Application No. 2001-64413) and those that define the association of water-soluble dyes (Japanese Patent Application No. 2001-117350).

  Regarding the relationship between the number of associative groups and the performance (ink absorbance of the ink), the introduction of the associative groups tends to cause a decrease in absorbance and a shorter wavelength of λmax even in a dilute solution. The relationship between the number of associative groups and the performance (reflection density OD on Epson PM920 image receiving paper) is that the reflection density OD at the same ionic strength decreases as the number of associative groups increases. In other words, the meeting seems to proceed on the image receiving paper. Regarding the relationship between the number of associative groups and the performance (ozone resistance / light resistance), the greater the number of associative groups, the better the ozone resistance. Dyes with a large number of associative groups tend to improve light resistance. In order to impart ozone resistance, it is necessary to impart a substituent to the benzene ring of phthalocyanine. Since the reflection density OD and the robustness are in a trade-off relationship, it is necessary to increase the light resistance without weakening the association.

A preferred embodiment of the cyan ink using the phthalocyanine dye having the above characteristics is as follows.
1) Dye remaining when xenon light (Xe 1.1 W / m (intermittent condition)) is irradiated with a TAC filter for 3 days at a site where the reflection density OD of the image printed on Epson PM photographic receiving paper is 1.0 Cyan ink with a rate of 90% or more.
2) The pigment residual ratio when the portion where the reflection density in the status A filter of the printed image is 0.9 to 1.1 is stored in a 5 ppm ozone environment for 24 hours is 60% or more (preferably 80% or more). Cyan ink.
3) A cyan ink in which the amount of Cu ions flowing out into water after ozone fading is 2% or less of the total dye.
4) Cyan ink that can penetrate up to 30% or more of the upper part of the image receiving layer of the specific image receiving paper.

  Examples of the dye having the above characteristics include a phthalocyanine dye represented by the general formula (2).

Phthalocyanine dyes are known as fast dyes, but are known to be inferior in fastness to ozone gas when used as inkjet recording dyes.
In the present invention, as described above, it is desirable to introduce an electron withdrawing group into the phthalocyanine skeleton to make the oxidation potential nobler than 1.0 V (vs SCE). Therefore, by introducing a substituent having a large Hammett's substituent constant σp value (a measure of electron withdrawing property or electron donating property) such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group, the oxidation potential can be made more noble. it can.
Also for the reason of such potential adjustment, it is preferable to use the phthalocyanine dye represented by the general formula (2).

Hereinafter, the phthalocyanine dye represented by the general formula (2) will be described in detail.
In the general formula (2), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are each independently —SO—Z ₂ , —SO ₂ —Z ₂ , —SO ₂ NR ₂₁ R ₂₂ , a sulfo group, —CONR ₂₁ R ₂₂ or —CO ₂ R ₂₁ is represented. Among these substituents, —SO—Z ₂ , —SO ₂ —Z ₂ , —SO ₂ NR ₂₁ R ₂₂ and —CONR ₂₁ R ₂₂ are preferable, and —SO ₂ —Z ₂ and —SO ₂ NR ₂₁ R are particularly preferable. ₂₂ is preferred, and —SO ₂ —Z ₂ is most preferred. Here, when any of a _{21 to} a ₂₄ representing the number of substituents represents a number of 2 or more, a plurality of X _{21 to} X ₂₄ may be the same or different, and each of the above is independently described above. Represents any group of X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ may all be the same substituent, or, for example, X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are all —SO ₂ —Z ₂ . And each Z ₂ includes different ones, which may be the same type of substituents but may be partially different from each other, or may be different from each other (for example, —SO ₂ —Z ₂ and it may include -SO ₂ NR ₂₁ R _22).

Z ₂ is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, Represents a substituted or unsubstituted heterocyclic group. Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred.

R ₂₁ and R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted It represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Of these, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group are preferable. Among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable. A cyclic group is more preferable. However, it is not preferred that both R ₂₁ and R ₂₂ are hydrogen atoms.

The substituted or unsubstituted alkyl group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably an alkyl group having 1 to 30 carbon atoms. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the same substituents as those described later when Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ can further have a substituent. Of these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they enhance the association of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group. The number of carbon atoms of the alkyl group does not include the carbon atom of the substituent, and the same applies to other groups.

The substituted or unsubstituted cycloalkyl group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably a cycloalkyl group having 5 to 30 carbon atoms. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferable because of increasing the solubility of the dye and the ink stability. Examples of the substituent include the same substituents as those described later when Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ can further have a substituent. Among these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they increase the association property of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted alkenyl group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably an alkenyl group having 2 to 30 carbon atoms. In particular, a branched alkenyl group is preferred because it increases the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the same substituents as those described later when Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ can further have a substituent. Among these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they increase the association property of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aralkyl group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably an aralkyl group having 7 to 30 carbon atoms. In particular, a branched aralkyl group is preferred because it increases the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the same substituents as those described later when Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ can further have a substituent. Among these, a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, and a sulfonamide group are particularly preferable because they increase the association property of the dye and improve the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ can further have a substituent. Among these, an electron-withdrawing group is particularly preferable because the oxidation potential of the dye is noble and fastness is improved. Examples of the electron-withdrawing group include those having a positive Hammett's substituent constant σp value. Among them, a halogen atom, a heterocyclic group, a cyano group, a carboxyl group, an acylamino group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, an acyl group, a sulfo group, and a quaternary ammonium group are preferable, and a cyano group , Carboxyl group, sulfamoyl group, carbamoyl group, sulfonyl group, imide group, acyl group, sulfo group, and quaternary ammonium group are more preferable.

The heterocyclic group represented by R ₂₁ , R ₂₂ and Z ₂ is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. In the following, the heterocyclic group represented by R ₂₁ , R ₂₂ and Z ₂ is exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. For example, if it is pyridine, Substitution at the 2nd, 3rd and 4th positions is possible. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benz Examples include isothiazole and thiadiazole. They may have a substituent, and as examples of the substituent, Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ described later can further have a substituent. In this case, the same substituents as those described above can be used. Preferred substituents are the same as those of the aryl group, and more preferred substituents are the same as the more preferred substituent of the aryl group.

Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, Acyl group, carboxy It can be exemplified group or a sulfo group, each of which may further have a substituent.
Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group are preferable. In particular, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group and a sulfo group are preferable, and a hydrogen atom is most preferable.

When Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ are groups that can further have a substituent, they may further have the following substituents.
A linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, and a linear chain having 2 to 12 carbon atoms Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in the dye) Preferred are those having an asymmetric carbon, and particularly preferred are those having an asymmetric carbon, such as methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2- Ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (eg, chlorine atom, bromine atom), aryl group (For example, phenyl, 4-t-butylphenyl, 2,4
-Di-t-amylphenyl), a heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, An amino group, an alkyloxy group (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (for example, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (for example, methylamino, Butylamino, di Tilamino, methylbutylamino), anilino group (eg, phenylamino, 2-chloroanilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N -Dipropylsulfamoylamino), alkylthio groups (eg methylthio, octylthio, 2-phenoxyethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), Alkyloxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N Dibutylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl) , Alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxy) Phenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-pheny) Rucarbamoyloxy), silyloxy groups (eg trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (eg phenoxycarbonylamino), imide groups (eg N-succinimide, N-phthalimide), heterocyclic thio groups ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg Carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  When the phthalocyanine dye represented by the general formula (2) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the dye and improves the ink stability.

  The number of ionic hydrophilic groups is preferably at least two in one molecule of phthalocyanine dye, and particularly preferably at least two sulfo groups and / or carboxyl groups.

In the general formula (2), a ₂₁ ~a ₂₄ and b ₂₁ ~b ₂₄ each represent the number of substituents of X ₂₁ to X ₂₄ and Y ₂₁ to Y _24. a _{21 to} a ₂₄ each independently represents an integer of 0 to 4, but they are not all 0 at the same time. b ₂₁ ~b ₂₄ each independently represents an integer of 0-4. When any of a _{21 to} a ₂₄ and b _{21 to} b ₂₄ is an integer of 2 or more, any one of X _{21 to} X ₂₄ and Y _{21 to} Y ₂₄ is present, May be the same as or different from each other.

a ₂₁ and b ₂₁ satisfy the relationship a ₂₁ + b ₂₁ = 4. Particularly preferred, a ₂₁ represents 1 or 2, a combination of b ₂₁ represents 3 or 2, Among them, a ₂₁ represents 1, b ₂₁ are the most preferred combination representing the three.

Each combination of a ₂₂ and b ₂₂ , a ₂₃ and b ₂₃ , and a ₂₄ and b ₂₄ has the same relationship as the combination of a ₂₁ and b ₂₁ , and a preferable combination is also the same.

M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof.
What is preferable as M is a metal element other than a hydrogen atom, such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Preferred examples of the oxide include VO and GeO.

Moreover, as a hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc. are mentioned preferably.

Further, examples of the halide include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl.

  Of these, Cu, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

  Further, in the phthalocyanine dye represented by the general formula (2), Pc (phthalocyanine ring) is a dimer (for example, Pc-MLMMM-Pc) or 3 via L (a divalent linking group). A monomer may be formed, and M at that time may be the same or different.

In this case, the divalent linking group represented by L is an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, or a methylene group —CH. _2- and the groups formed by combining these are preferred.

  As for the preferable combination of substituents of the compound represented by the general formula (2), a compound in which at least one of various substituents is the above-mentioned preferable group is preferable, and more various substituents are the above-mentioned preferable groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

Among the phthalocyanine dyes represented by the general formula (2), a phthalocyanine dye having a structure represented by the following general formula (5) is more preferable. Hereinafter, the phthalocyanine dye represented by the general formula (5) will be described in detail.
General formula (5)

In Formula _{(5), X 51 ~X 54} , Y 51 ~Y 58 is the general formula _{X 21 ~X 24, Y 21 ~Y} 24 in (2) the same meanings, preferred examples are also the same is there. Further, M ₁ is the same meaning as M in formula (2), preferred examples are also the same.

In the general formula (5), a _{51 to} a ₅₄ are each independently an integer of 1 or 2, preferably satisfying 4? A ₅₁ + a ₅₂ + a ₅₃ + a ₅₄ ? 6, particularly preferably a ₅₁ = a _{This is when 52} = a ₅₃ = a ₅₄ = 1.

X ₅₁ , X ₅₂ , X ₅₃ and X ₅₄ may each be exactly the same substituent, or, for example, X ₅₁ , X ₅₂ , X ₅₃ and X ₅₄ are all —SO ₂ —Z ₂ and each As in the case where Z ₂ includes different ones, they may be the same type of substituents but may be partially different from each other, or different from each other, for example, —SO ₂ —Z ₂ and —SO _{2. 2} NR ₂₁ R ₂₂ may be included.

Among the phthalocyanine dyes represented by the general formula (5), particularly preferred combinations of substituents are as follows.
X _{51 to} X ₅₄ are each independently preferably —SO—Z ₂ , —SO ₂ —Z ₂ , —SO ₂ NR ₂₁ R ₂₂ or —CONR ₂₁ R ₂₂ , and in particular —SO ₂ —Z ₂ or — SO ₂ NR ₂₁ R ₂₂ is preferred, and —SO ₂ —Z ₂ is most preferred.

Z ₂ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and most preferably a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. . In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.

R ₂₁ and R ₂₂ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom and a substituted alkyl A group, a substituted aryl group, and a substituted heterocyclic group are more preferable. However, it is not preferred that both R ₂₁ and R ₂₂ are hydrogen atoms. In particular, the case of having an asymmetric carbon in the substituent (use in a racemic form) is preferable because of increasing the solubility of the dye and the ink stability. In addition, for the reason of increasing the association property and improving the fastness, it is preferable that a hydroxyl group, an ether group, an ester group, a cyano group, an amide group, or a sulfonamide group have in the substituent.

Y _{51 to} Y ₅₈ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl And a sulfo group are preferable, and a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfo group is particularly preferable, and a hydrogen atom is most preferable.

a _{51 to} a ₅₄ are each independently preferably 1 or 2, and particularly preferably all 1.

M ₁ represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, particularly Cu, Ni, Zn, and Al, and particularly Cu is most preferable.

When the phthalocyanine dye represented by the general formula (5) is water-soluble, it preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, an alkali metal salt is preferable, and a lithium salt is particularly preferable because it increases the solubility of the dye and improves the ink stability.

  As the number of ionic hydrophilic groups, it is preferable to have at least two phthalocyanine dye molecules, and it is particularly preferable to have at least two sulfo groups and / or carboxyl groups.

  As for the preferred combination of substituents of the compound represented by the general formula (5), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  As the chemical structure of the phthalocyanine dye represented by the general formula (5), at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group is added to each of the four benzene rings of the phthalocyanine. It is preferable to introduce so that the total of the σp values of all substituents is 1.6 or more.

  Here, Hammett's substituent constant σp value will be described briefly. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. In addition, dyes used in the present invention include those that are not benzene derivatives, but the σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense.

The phthalocyanine dye represented by the general formula (2) inevitably has different introduction positions and introduction numbers of substituents Xn (n = 1 to 4) and Ym (m = 1 to 4) depending on the synthesis method. Mixtures are common, so the general formula often represents a statistical average of these analog mixtures. In the present invention, it has been found that a specific mixture is particularly preferable when these analog mixtures are classified into the following three types. That is, the phthalocyanine dye analog mixture represented by the general formulas (2) and (5) is defined by classifying into the following three types based on the substitution position. In the general formula (5), Y ₅₁ , Y ₅₂ , Y ₅₃ , Y ₅₄ , Y ₅₅ , Y ₅₆ , Y ₅₇ , Y ₅₈ are set to positions 1, 4, 5, 8, 9, 12, 13, 16 respectively. .

(1) β-position substitution type: phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position.
(2) α-position substitution type: phthalocyanine dye having a specific substituent at 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position.
(3) α, β-position mixed substitution type: a phthalocyanine dye having a specific substituent without regularity at positions 1 to 16.

  In the present specification, when describing derivatives of phthalocyanine dyes having different structures (particularly, different substitution positions), the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used. .

  Examples of the phthalocyanine dye used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored, published by VCH, “Phthalogicanes-Properties and Applications” (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

  The phthalocyanine dye represented by the general formula (2) of the present invention is described in International Publication Nos. 00/17275, 00/08103, 00/08101, 98/41853, and JP-A-10-36471. As described above, for example, it can be synthesized through sulfonation, sulfonyl chlorideation, and amidation reaction of an unsubstituted phthalocyanine compound. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, since the number and position of the heterocyclic-substituted sulfamoyl group cannot be specified when synthesizing it as a raw material, the resulting phthalocyanine dye includes α, β-, which includes several kinds of compounds having different numbers and positions of substituents. It is obtained as a coordinate mixed substitution type mixture.

  As described above, for example, when a large number of electron withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and the ozone resistance is enhanced. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.

  The phthalocyanine compound represented by the general formula (5) of the present invention is, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula represented by the general formula (6). Derived from a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalonitrile derivative (compound R) represented by the following formula with a metal derivative represented by the following general formula (6): can do.

In the above formulas, Xp corresponds to X ₅₁ , X ₅₂ , X ₅₃ or X ₅₄ in the general formula (5). Yq and Yq ′ correspond to Y ₅₁ , Y ₅₂ , Y ₅₃ , Y ₅₄ , Y ₅₅ , Y ₅₆ , Y ₅₇ or Y ₅₈ in the general formula (5), respectively. In compound R, M ′ represents a cation.

  Examples of the cation represented by M ′ include alkali metal ions such as Li, Na, and K, or organic cations such as triethylammonium ion and pyridinium ion.

  General formula (6): M- (Y) d

In the general formula (6), M is synonymous with M in the general formula (2) and M _{1 in the} general formula (5), and Y is monovalent such as a halogen atom, an acetate anion, acetylacetonate, oxygen and the like. Or a bivalent ligand is shown, d is an integer of 1-4.

  That is, according to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when it is desired to introduce a large number of electron withdrawing groups in order to make the oxidation potential noble as in the present invention, the above synthesis method is the method already described for synthesizing the phthalocyanine compound of the general formula (2). It is extremely superior compared to

  The phthalocyanine compound represented by the general formula (5) thus obtained is usually a mixture of compounds represented by the following general formulas (a) -1 to (a) -4 which are isomers at each substitution position of Xp. That is, the β-position substitution type.

In the above synthesis method, if the same Xp is used, a β-position substituted phthalocyanine dye in which X ₅₁ , X ₅₂ , X ₅₃ and X ₅₄ are the same substituents can be obtained. On the other hand, by using different combinations of Xp, it is possible to synthesize dyes having the same type of substituents but partially different from each other, or dyes having different types of substituents. . Among the dyes of the general formula (5), these dyes having mutually different electron-withdrawing substituents are particularly preferable because they can adjust the solubility of the dye, the associability, the stability with time of the ink, and the like.

  In the present invention, it is found that it is very important to improve the fastness that the oxidation potential is noble than 1.0 V (vs SCE) in any substitution type. It was completely unpredictable from the prior art. Although the cause is unknown in detail, the β-position substitution type is clearly superior in terms of hue, light fastness, ozone gas resistance, etc. than the α, β-position mixed substitution type. there were.

  Specific examples of the phthalocyanine dyes represented by the general formulas (2) and (5) (Exemplary compounds I-1 to I-12 and 101 to 190) are shown below. The phthalocyanine dyes used in the present invention are as follows. It is not limited to the example.

  In addition, the structure of the phthalocyanine compound shown by M-Pc (Xp1) m (Xp2) n of compound Nos. 146 to 190 is as follows.

  The phthalocyanine dye represented by the general formula (2) can be synthesized according to the aforementioned patent. Moreover, the phthalocyanine dye represented by the general formula (5) is not limited to the above-described synthesis method, and JP-A Nos. 2001-226275, 2001-96610, 2001-47013, and 2001-193638. It can be synthesized by the method described in 1. Further, the starting material, the dye intermediate and the synthesis route are not limited to these.

  The content of the phthalocyanine dye represented by the general formula (2) in the ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

[Magenta dye]
The magenta dye used in the present invention is preferably an azo dye having an absorption maximum in a spectral region of 500 to 580 nm in an aqueous medium and having an oxidation potential nobler than 1.0 V (vs SCE).

  The first structural feature of the preferred dye of the azo dye, which is a magenta dye, is a dye having a chromophore represented by the general formula (heterocycle A) -N = N- (heterocycle B). is there. In this case, the heterocyclic ring A and the heterocyclic ring B may have the same structure. Heterocycle A and heterocycle B are specifically 5-membered or 6-membered heterocycles, such as pyrazole, imidazole, triazole, oxazole, thiazol, selenazole, It is a heterocyclic ring selected from pyridone, pyrazine, pyrimidine and pyridine. Specific examples are described in JP-A No. 2001-279145, JP-A No. 2002-309116, JP-A No. 2003-12650, and the like.

  Further, a second preferred structural feature of the azo dye is that the azo group is an azo dye in which an aromatic nitrogen-containing 6-membered heterocyclic ring is directly connected to at least one of them as a coupling component. Is described in JP-A-2002-371214.

  A third preferred structural feature is that the auxiliary color group has a structure of an aromatic ring amino group or a heterocyclic amino group, specifically an anilino group or a heterylamino group.

  A fourth preferred structural feature is that it has a three-dimensional structure. Specifically, it is described in Japanese Patent Application No. 2002-12015.

  By imparting the above structural characteristics to the azo dye, the oxidation potential of the dye can be increased and the ozone resistance can be improved. As a means for increasing the oxidation potential, it is possible to remove α hydrogen of the azo dye. Moreover, the azo dye of General formula (3) is a preferable dye also from a viewpoint of raising an oxidation potential. The means for increasing the oxidation potential of the azo dye is specifically described in Japanese Patent Application No. 2001-254878.

  The magenta ink of the present invention using the azo dye having the above characteristics is excellent in terms of hue that λmax (absorption maximum wavelength) is 500 to 580 nm, and further, on the long wave side and the short wave side of the maximum absorption wavelength. It is preferable that the half width is small, that is, sharp absorption. Specifically, it is described in JP-A No. 2002-309133. Further, sharpening of absorption can be realized by introducing a methyl group at the α-position using the azo dye of the general formula (3).

The forced fading rate constant of the magenta ink using the azo dye with respect to ozone gas is preferably 5.0 × 10 ⁻² [hour ⁻¹ ] or less, more preferably 3.0 × 10 ⁻² [hour ⁻¹ ]. 1.5 × 10 ⁻² [hour ⁻¹ ] or less is particularly preferable.
The forced fading rate constant for ozone gas is determined by measuring the color of the main spectral absorption region of the ink obtained by printing only the magenta ink on the reflective image receiving medium, and the reflection density measured through the status A filter. A colored region having a density of 0.90 to 1.10 is selected as an initial density point, and this initial density is set as a starting density (= 100%). This image is faded using an ozone fading tester that constantly maintains an ozone concentration of 5 mg / L, the time until the concentration reaches 80% of the initial concentration is measured, and the reciprocal of this time [hour ^-1 ] is calculated. The amber reaction rate constant is obtained on the assumption that the relationship between the amber color density and the time follows the rate equation of the first order reaction.
As the test print patch, a patch printed with a black square symbol of JIS code 2223, a stepped color patch of Macbeth chart, or any other step density patch that can obtain a measurement area can be used.
The reflection density of the reflected image (stepped color patch) printed for measurement is the density obtained with the measurement light that has passed through the status A filter by a densitometer that satisfies the international standard ISO5-4 (geometric condition of reflection density). It is.
The test chamber for measuring the forced fading rate constant for ozone gas is provided with an ozone generator (for example, a high-pressure discharge system that applies an AC voltage to dry air) that can constantly maintain the internal ozone gas concentration at 5 mg / L, The aeration temperature is adjusted to 25 ?.
This forced fading rate constant is determined by the susceptibility to oxidation by an oxidizing atmosphere in the environment, such as photochemical smog, automobile exhaust, organic vapor from painted surfaces and carpets of furniture, and gas generated in the frame of a bright room. An index that represents these oxidizing atmospheres with ozone gas.

Below, the dye which has the said characteristic and is represented by General formula (3) which is an azo dye used by this invention is demonstrated.
In the general formula (3), A represents a 5-membered heterocyclic group.
B ₃₁ and B ₃₂ are each, = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - or represents a -CR ₃₂ =.
R ₃₅ and R ₃₆ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, It represents an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted.

G, R ₃₁ and R ₃₂ each independently represent a hydrogen atom or a substituent, and the substituent is a halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, Alkylthio group, a Represents a thio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and the hydrogen atom of each substituent May be further substituted.
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- to 6-membered ring.

In the general formula (3), A represents a 5-membered heterocyclic group, and examples of the heterocyclic hetero atom include N, O, and S. A nitrogen-containing 5-membered heterocyclic ring is preferable, and an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed to the heterocyclic ring.
Examples of preferred heterocyclic rings for A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, pyrazole rings, imidazole rings, isothiazole rings, thiadiazole rings, and benzothiazole rings represented by the following general formulas (a) to (f) are preferable.

In the following general formulas (a) to (f), R ₃₀₇ to R ₃₂₀ represent the same substituents as G, R ₃₁ and R ₃₂ in the general formula (3).
Of the general formulas (a) to (f), preferred are the pyrazole ring and isothiazole ring represented by the general formulas (a) and (b), and the most preferred is represented by the general formula (a). It is a pyrazole ring.

In the general formula (3), B ₃₁ and B ₃₂ each represent ═CR ₃₁ — and —CR ₃₂ ═, or either one represents a nitrogen atom, and the other represents ═CR ₃₁ — or —CR ₃₂ ═. Are more preferable to represent ═CR ₃₁ — and —CR ₃₂ ═, respectively.

R ₃₅ and R ₃₆ are preferably a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. The hydrogen atom of each substituent may be substituted. However, _R35 and _R36 are not simultaneously hydrogen atoms.

  G is a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group, acylamino group, ureido group, sulfamoylamino group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, amino is more preferable. A hydrogen atom, an amino group (preferably an anilino group), and an acylamino group. The hydrogen atom of each substituent may be substituted.

Preferable examples of R ₃₁ and R ₃₂ include a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group, and a cyano group. The hydrogen atom of each substituent may be substituted.
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- to 6-membered ring.

When A has a substituent, or when the substituent of R ₃₁ , R ₃₂ , R ₃₅ , R ₃₆ or G further has a substituent, the substituents described above for G, R ₃₁ and R ₃₂ The group can be mentioned.

When the dye represented by the general formula (3) is a water-soluble dye, an ionic hydrophilic group is further added as a substituent at any position on A, R ₃₁ , R ₃₂ , R ₃₅ , R ₃₆ , and G. It preferably has a functional group. Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).

  Here, terms (substituents) used in the description of the general formula (3) will be described. These terms are common to general formula (3) and general formula (3-A) described later.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

An aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The term “substituted” used for “substituted alkyl group” and the like indicates that a hydrogen atom present in the “alkyl group” or the like is substituted with the substituents mentioned in the above G, R ₃₁ and R ₃₂ .

  The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl moiety of the aralkyl group and the substituted aralkyl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl Group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.

An aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The number of carbon atoms in the aromatic group is preferably 6 to 20, and more preferably 6 to 16.
Examples of the aromatic group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group.

  The heterocyclic group includes a substituted heterocyclic group. In the heterocyclic group, an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed with the heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, an ionic hydrophilic group, and the like. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group and 2-furyl group.

  The carbamoyl group includes a substituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The alkoxycarbonyl group includes a substituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The aryloxycarbonyl group includes a substituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The heterocyclic oxycarbonyl group includes a substituted heterocyclic oxycarbonyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.

  The acyl group includes a substituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

  The alkoxy group includes a substituted alkoxy group. As said alkoxy group, a C1-C20 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The aryloxy group includes a substituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The heterocyclic oxy group includes a substituted heterocyclic oxy group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

  The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

  The acyloxy group includes a substituted acyloxy group. The acyloxy group is preferably an acyloxy group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a substituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

  The aryloxycarbonyloxy group includes a substituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

  The amino group includes a substituted amino group. The substituent includes an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent. The alkylamino group includes a substituted alkylamino group. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The arylamino group includes a substituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include a phenylamino group and a 2-chlorophenylamino group.

  The heterocyclic amino group includes a substituted heterocyclic amino group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic amino group is preferably a heterocyclic amino group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.

  The acylamino group includes a substituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The ureido group includes a substituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group includes a substituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  The alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The aryloxycarbonylamino group includes a substituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The alkylsulfonylamino group and the arylsulfonylamino group include a substituted alkylsulfonylamino group and a substituted arylsulfonylamino group. The alkylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonylamino group having 1 to 20 carbon atoms and an arylsulfonylamino group. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylsulfonylamino group and arylsulfonylamino group include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.

  The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thienylsulfonylamino group and a 3-pyridylsulfonylamino group.

  The alkylthio group, arylthio group and heterocyclic thio group include a substituted alkylthio group, a substituted arylthio group and a substituted heterocyclic thio group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The alkylthio group, arylthio group and heterocyclic thio group are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group, arylthio group and heterocyclic thio group include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  The alkylsulfonyl group and arylsulfonyl group include a substituted alkylsulfonyl group and a substituted arylsulfonyl group. Examples of the alkylsulfonyl group and the arylsulfonyl group can include a methylsulfonyl group and a phenylsulfonyl group, respectively.

  The heterocyclic sulfonyl group includes a substituted heterocyclic sulfonyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thienylsulfonyl group and a 3-pyridylsulfonyl group.

  The alkylsulfinyl group and the arylsulfinyl group include a substituted alkylsulfinyl group and a substituted arylsulfinyl group. Examples of the alkylsulfinyl group and the arylsulfinyl group include a methylsulfinyl group and a phenylsulfinyl group, respectively.

  The heterocyclic sulfinyl group includes a substituted heterocyclic sulfinyl group. Examples of the heterocyclic ring include the heterocyclic rings described in the heterocyclic group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include a 4-pyridylsulfinyl group.

  The sulfamoyl group includes a substituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Of the general formula (3), a particularly preferred structure is represented by the following general formula (3-A).
Formula (3-A);

In the formula, R ₃₁ , R ₃₂ , R ₃₅ and R ₃₆ have the same _{meanings as those} in the general formula (3).
R ₃₃ and R ₃₄ each independently represents a hydrogen atom or a substituent, and the substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Represents an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; Of these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, or a heterocyclic group is particularly preferable.

Z ₃₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₃₁ is preferably an electron-withdrawing group having a σp value of 0.30 or more, more preferably an electron-withdrawing group of 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. It is desirable not to exceed zero.

  Specifically, examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methylsulfonyl group and an arylsulfonyl group (for example, a phenylsulfonyl group)). Can be mentioned.

  In addition to the above, an electron-withdrawing group having a Hammett substituent constant σp value of 0.45 or more includes an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m- Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated An alkyl group (for example, trifluoromethyl) can be mentioned.

  As the electron-withdrawing group having a Hammett substituent constant σp value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), halogen Alkoxy group (for example, trifluoromethyloxy), halogenated aryloxy group (for example, pentafluorophenyloxy), sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group (for example, difluoromethylthio), 2 An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with one or more electron-withdrawing groups having a σp value of 0.15 or more, and a heterocycle (eg, 2-benzoxazolyl, 2- Benzothiazolyl, 1-phenyl-2-benzimidazolyl) be able to.

  Specific examples of the electron-withdrawing group having a Hammett substituent constant σp value of 0.20 or more include a halogen atom in addition to the above.

Z ₃₁ is, among the above, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A 20 arylsulfonyl group, a carbamoyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

Z ₃₂ represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group or a heterocyclic group. Z ₃₂ is preferably an aliphatic group, more preferably an alkyl group having 1 to 6 carbon atoms.

  Q represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a heterocyclic group. Among them, Q is preferably a group consisting of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. The 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Of these, aromatic groups and heterocyclic groups are particularly preferred. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms or carbon atoms. Specific examples of such a ring structure include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring. , Benzimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thiane ring.

The hydrogen atom of each substituent described in the general formula (3-A) may be substituted. Examples of the substituent include the substituents described in the general formula (3), the groups exemplified for G, R ₃₁ and R ₃₂ , and ionic hydrophilic groups.

A particularly preferred combination of substituents as the azo dye represented by the general formula (3) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ₃₅ and R ₃₆ . More preferred are a hydrogen atom, an aryl group, a heterocyclic group, and a sulfonyl group, and most preferred are a hydrogen atom, an aryl group, and a heterocyclic group. However, R ₃₅ and R ₃₆ are not both hydrogen atoms.

  G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom or an amino group. An acylamino group.

  Among A, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring are preferable, a pyrazole ring and an isothiazole ring are further preferable, and a pyrazole ring is most preferable.

B ₃₁ and B ₃₂ are ═CR ₃₁ — and —CR ₃₂ ═, respectively, and R ₃₁ and R ₃₂ are preferably hydrogen atom, alkyl group, halogen atom, cyano group, carbamoyl group, carboxyl group, hydroxyl group, alkoxy group, respectively. Group, an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group, or a carbamoyl group.

  In addition, about the preferable combination of a substituent of the compound represented by the said General formula (3), the compound whose at least 1 of a various substituent is the said preferable group is preferable, and many more various substituents are the said preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  Specific examples of the azo dye represented by the general formula (3) are shown below, but the present invention is not limited to the following examples.

  The content of the azo dye represented by the general formula (3) in the ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass. Further, the solubility in water (or dispersion degree in a stable state) at 20? Is preferably 5% by mass or more, more preferably 10% by mass or more.

[Black dye]
The black ink used in the present invention has a wavelength λmax of 500 nm to 700 nm, and a half-value width (Wλ _{, 1/2} ) in an absorption spectrum of a diluted solution normalized to an absorbance of 1.0 is 100 nm or more (preferably 120 nm or more). A dye (L) that is 500 nm or less, more preferably 120 nm or more and 350 nm or less) is used.

  If this dye (L) alone can achieve high image quality “(good) black” = black that does not depend on the observation light source and any of the color tones of B, G, and R is difficult to emphasize, Although it is possible to use the dye alone as a black ink dye, it is generally used in combination with a dye that covers a region where the absorption of the dye is low. Usually, it is preferably used in combination with a dye (S) having a main absorption (λmax of 350 to 500 nm) in the yellow region. Further, it is possible to produce a black ink in combination with another dye.

  In the present invention, a black ink is prepared by dissolving or dispersing the dye alone or in a water-based medium. The black ink for ink jet recording has preferable performance, that is, 1) excellent weather resistance, and 2) In order to satisfy that the black balance is not lost even after fading, it is preferable to prepare an ink that satisfies the following conditions.

First, the black square number of the JIS code 2223 is printed at 48 points using the black ink, and the reflection density (D _vis ) measured by the status A filter (visual filter) is defined as the initial density. An example of a reflection density measuring machine equipped with a status A filter is an X-Rite density measuring machine. Here, when measuring the density of “black”, the measured value by D _vis is used as the standard observation reflection density. This printed matter is forcibly faded using an ozone fading tester capable of always generating 5 ppm of ozone, and forced from the time (t) until the reflection density (D _vis ) reaches 80% of the initial reflection density value. The fading rate constant (k _vis ) is obtained from the relational expression “0.8 = exp (−k _vis · t)”.
In the black ink, the rate constant (k _vis ) is preferably 5.0 × 10 ⁻² [hour ⁻¹ ] or less, more preferably 3.0 × 10 ⁻² [hour ⁻¹ ] or less, and 1.0 × 10. ^-2 [hour ^-1 ] or less is particularly preferable. (Condition 1)

In addition, the black square symbol of the JIS code 2223 is printed at 48 points using the black ink, and this is a density measurement value measured by the status A filter, which is not D _vis , C (cyan), M (magenta), Y The reflection density (D _R , D _G , D _B ) of the three colors (yellow) is also defined as the initial density. Here, (D _R , D _G , D _B ) indicates (C reflection density by the red filter, M reflection density by the green filter, and Y reflection density by the blue filter). This printed matter was forcibly faded using an ozone fading tester capable of always generating 5 ppm of ozone according to the above method, and each reflection density (D _R , D _G , D _B ) was 80% of the initial density value. Similarly, the forced fading rate constants (k _R , k _G , k _B ) are determined from the time until When the three rate constants are obtained and the ratio (R) between the maximum value and the minimum value is obtained (for example, when k _R is the maximum value and k _G is the minimum value, R = k _R / k _G ), The ratio (R) is preferably 1.2 or less, more preferably 1.1 or less, and particularly preferably 1.05 or less. (Condition 2)

  Note that the “printed matter in which the black square symbol of the JIS code 2223 is printed at 48 points” used above gives an image large enough to cover the aperture of the measuring instrument in order to give a sufficient size for density measurement. It is printed.

  Further, as described above, the oxidation potential of at least one dye used in the black ink is noble than 1.0 V (vs SCE), preferably noble than 1.1 V (vs SCE), more preferably 1.2 V. It is more noble than (vs SCE), most preferably no less than 1.25 V (vs SCE), and at least one of the dyes preferably has a λmax of 500 nm or more. (Condition 3)

  Further, the black ink is prepared using the azo dye described in the general formula (4). The azo dye described in the general formula (4) first corresponds to a dye (L) having a λmax of 500 nm to 700 nm and a half-value width of 100 nm or more in an absorption spectrum of a diluted solution normalized to an absorbance of 1.0. Things can be mentioned. In addition to this, the dye (S) having a λmax of 350 nm to 500 nm can also be cited as corresponding to the dye of the general formula (4). Preferably, at least one of the dyes (L) is a dye of the general formula (4), particularly preferably at least one of the dyes (L) and (S) is a dye of the general formula (4), It is preferable that 90% by mass of the total dye in the ink is the dye of the general formula (4). (Condition 4)

  The black ink in the present invention is a black ink that satisfies at least one of the above conditions 1 to 4.

Hereinafter, the dye represented by the general formula (4) will be described.
In the general formula (4), A ₄₁ , B ₄₁ and C ₄₁ each independently represents an optionally substituted aromatic group or an optionally substituted heterocyclic group (A ₄₁ and C ₄₁ represent one And B ₄₁ is a divalent group).
m is 1 or 2, n is an integer of 0 or more, and preferably m = n = 1.
The azo dye represented by the general formula (4) is particularly preferably a dye represented by the following general formula (4-A).
Formula (4-A);

In the general formula (4-A), A ₄₁ and B ₄₁ have the same _{meaning as} in the general formula (4). B ₄₂ and B ₄₃ are each = CR ₄₁ - represents a or -CR ₄₂ = - and -CR ₄₂ = or represents, or one nitrogen atom and the other = CR _41.

G ₄ , R ₄₁ and R ₄₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group , Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkyl Amino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group , Nito A group, an alkyl or arylthio group, a heterocyclic thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, each group being further substituted May be.

R ₄₅ and R ₄₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group. Each group may further have a substituent. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms.
R ₄₁ and R ₄₅ , or R ₄₅ and R ₄₆ may be bonded to form a 5- to 6-membered ring.

The azo dye represented by the general formula (4-A) is preferably a dye represented by the following general formula (4-B).
Formula (4-B);

In formula (4-B), R ₄₇ and R ₄₈ have the same meaning as R ₄₁ in formula (4-A).

  Here, the term (substituent) used in the description of the general formula (4), the general formula (4-A), and the general formula (4-B) will be described. These terms are common to the description of the general formula (4-C) and general formula (4-D) described later.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  An aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The aliphatic group may have a branch and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl group, benzyl group, 2-phenethyl Groups, vinyl groups, and allyl groups.

  The monovalent aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. The monovalent aromatic group preferably has 6 to 20 carbon atoms, more preferably 6 to 16. Examples of the monovalent aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl. The divalent aromatic group is a divalent version of these monovalent aromatic groups. Examples thereof include phenylene, p-tolylene, p-methoxyphenylene, o-chlorophenylene, and m- (3 -Sulfopropylamino) phenylene, naphthylene and the like.

  The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and N, O, and S can be exemplified as the hetero atom of the heterocyclic ring. Examples of the substituent include aliphatic groups, halogen atoms, alkyl and arylsulfonyl groups, acyl groups, acylamino groups, sulfamoyl groups, carbamoyl groups, ionic hydrophilic groups, and the like. Examples of heterocyclic rings used for monovalent and divalent heterocyclic groups include pyridine, thiophene, thiazole, benzothiazole, benzoxazole, and furan ring.

  The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group. Examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.

  The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The heterocyclic oxycarbonyl group includes a heterocyclic oxycarbonyl group having a substituent and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group is preferably a heterocyclic oxycarbonyl group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic oxycarbonyl group include a 2-pyridyloxycarbonyl group.
The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

  The alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As an alkoxy group, a C1-C20 alkoxy group is preferable. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  The aryloxy group includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The heterocyclic oxy group includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having 2 to 20 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, and an ionic hydrophilic group. Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 3-thienyloxy group.

  The silyloxy group is preferably a silyloxy group substituted with an aliphatic group or aromatic group having 1 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.

  The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The alkoxycarbonyloxy group includes an alkoxycarbonyloxy group having a substituent and an unsubstituted alkoxycarbonyloxy group. As the alkoxycarbonyloxy group, an alkoxycarbonyloxy group having 2 to 20 carbon atoms is preferable. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group and an isopropoxycarbonyloxy group.

  The aryloxycarbonyloxy group includes an aryloxycarbonyloxy group having a substituent and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 20 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group.

The amino group includes an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, aryl group and heterocyclic group may further have a substituent. As the alkylamino group, an alkylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The arylamino group includes an arylamino group having a substituent and an unsubstituted arylamino group. The arylamino group is preferably an arylamino group having 6 to 20 carbon atoms. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamino group include an anilino group and a 2-chlorophenylamino group.
The heterocyclic amino group includes a heterocyclic amino group having a substituent and an unsubstituted heterocyclic amino group. As the heterocyclic amino group, a heterocyclic amino group having 2 to 20 carbon atoms is preferable. Examples of the substituent include an alkyl group, a halogen atom, and an ionic hydrophilic group.

  The acylamino group includes an acylamino group having a substituent and an unsubstituted acylamino group. The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido group having 1 to 20 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group. Examples of the substituent include an alkyl group. Examples of the sulfamoylamino group include N, N-dipropylsulfamoylamino group.

  The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

  The alkyl and arylsulfonylamino groups include substituted alkyl and arylsulfonylamino groups, and unsubstituted alkyl and arylsulfonylamino groups. As the sulfonylamino group, a sulfonylamino group having 1 to 20 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of these sulfonylamino groups include a methylsulfonylamino group, an N-phenyl-methylsulfonylamino group, a phenylsulfonylamino group, and a 3-carboxyphenylsulfonylamino group.

  The heterocyclic sulfonylamino group includes a heterocyclic sulfonylamino group having a substituent and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group is preferably a heterocyclic sulfonylamino group having 1 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonylamino group include a 2-thiophenesulfonylamino group and a 3-pyridinesulfonylamino group.

  The heterocyclic sulfonyl group includes a heterocyclic sulfonyl group having a substituent and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group is preferably a heterocyclic sulfonyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfonyl group include a 2-thiophenesulfonyl group and a 3-pyridinesulfonyl group.

  The heterocyclic sulfinyl group includes a heterocyclic sulfinyl group having a substituent and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group is preferably a heterocyclic sulfinyl group having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic sulfinyl group include a 4-pyridinesulfinyl group.

  The alkyl, aryl and heterocyclic thio groups include substituted alkyl, aryl and heterocyclic thio groups and unsubstituted alkyl, aryl and heterocyclic thio groups. Alkyl, aryl and heterocyclic thio groups are preferably those having 1 to 20 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  The alkyl and arylsulfonyl groups include substituted alkyl and arylsulfonyl groups, unsubstituted alkyl and arylsulfonyl groups. Examples of alkyl and arylsulfonyl groups include methylsulfonyl and phenylsulfonyl groups, respectively.

  Alkyl and arylsulfinyl groups include substituted alkyl and arylsulfinyl groups, unsubstituted alkyl and arylsulfinyl groups. Examples of alkyl and arylsulfinyl groups include methylsulfinyl group and phenylsulfinyl group, respectively.

  The sulfamoyl group includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group. Examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Next, general formulas (4), (4-A) and (4-B) will be further described.
In the following description, what has already been described applies to the group and the substituent.
In the general formula (4), A ₄₁ , B ₄₁ and C ₄₁ are each independently an optionally substituted aromatic group (A ₄₁ and C ₄₁ are monovalent aromatic groups such as an aryl group; B ₄₁ represents a divalent aromatic group such as an arylene group) or an optionally substituted heterocyclic group (A ₄₁ and C ₄₁ are monovalent heterocyclic groups; B ₄₁ is a divalent heterocyclic group). Examples of the aromatic ring include a benzene ring and a naphthalene ring, and examples of the hetero atom of the heterocyclic ring include N, O, and S. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
The substituent may be an arylazo group or a heterocyclic azo group.
At least one of A ₄₁ , B ₄₁ and C ₄₁ is preferably a heterocyclic group, and more preferably at least two of A ₄₁ , B ₄₁ and C ₄₁ are heterocyclic groups. Further, all of A ₄₁ , B ₄₁ and C ₄₁ may be a heterocyclic group.

A preferable heterocyclic group of C ₄₁ includes an aromatic nitrogen-containing 6-membered heterocyclic group represented by the following general formula (4-C). C ₄₁ is, if an aromatic nitrogen-containing 6-membered heterocyclic group represented by the following formula (4-C) is represented by the general formula (4) corresponds to the general formula (4-A).
Formula (4-C);

In the general formula (4-C), B ₄₂ and B ₄₃ each represent ═CR ₄₁ — and —CR ₄₂ ═, or either one is a nitrogen atom, and the other is ═CR ₄₁ — or —CR ₄₂ ═. Represents. Each, = CR ₄₁ -, - represents a CR ₄₂ = is more preferable.
R ₄₅ and R ₄₆ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. Preferable substituents represented by R ₄₅ and R ₄₆ include a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkyl or arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, and a heterocyclic group. Each group may further have a substituent. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms.

G ₄ , R ₄₁ and R ₄₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group , Heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkyl Amino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group Nitro group It represents an alkyl or arylthio group, a heterocyclic thio group, an alkyl and arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, or a sulfo group, and each group may be further substituted. Good.

Examples of the substituent represented by G ₄ include a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, an amino group (an alkylamino group, Arylamino group, including heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylthio group, or heterocyclic thio group, more preferably Is a hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group) or acylamino group, and particularly a hydrogen atom Anilino group and acylamino group are most preferred. Each group may further have a substituent.

Preferable substituents represented by R ₄₁ and R ₄₂ include a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group, and a cyano group. Each group may further have a substituent.
R ₄₁ and R ₄₅ , or R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.
Examples of the substituent in the case where each substituent represented by A ₄₁ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ , G ₄ further has a substituent include the substituents exemplified in the above G ₄ , R ₄₁ , R ₄₂ The group can be mentioned. Moreover, it is preferable to further have an ionic hydrophilic group as a substituent at any position on A ₄₁ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ , and G ₄ .

  Examples of the ionic hydrophilic group as a substituent include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group and sulfo group may be in a salt state. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium). Among them, lithium ions are preferable.

Preferred heterocyclic rings when B ₄₁ has a ring structure include a thiophene ring, a thiazole ring, an imidazole ring, a benzothiazole ring, and a thienothiazole ring. Each heterocyclic group may further have a substituent. Of these, the thiophene ring, thiazole ring, imidazole ring, benzothiazole ring and thienothiazole ring represented by the following (a) to (e) are preferable. When B ₄₁ is a thiophene ring represented by (a) and C ₄₁ is a structure represented by the general formula (4-C), the general formula (4) is represented by the general formula (4-B ).

In the above formulas (a) to (e), R ₄₀₉ to R ₄₁₇ represent a substituent having the same meaning as G ₄ , R ₄₁ and R ₄₂ in the general formula (4-A).

Among the dyes represented by the general formula (4-B), a particularly preferable structure is one represented by the following general formula (4-D).
Formula (4-D);

In the formula, Z ₄ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₄ is preferably an electron-withdrawing group having a σp value of 0.30 or more, more preferably 0.45 or more, and particularly preferably an electron-withdrawing group of 0.60 or more. It is desirable not to exceed zero.

Specifically, Hammett substituent constant σp Examples of the electron withdrawing group having a value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group (for example, a methanesulfonyl group and an arylsulfonyl group (for example, a benzenesulfonyl group)).

  In addition to the above, an electron-withdrawing group having a Hammett substituent constant σp value of 0.45 or more includes an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m- Chlorophenoxycarbonyl), alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated An alkyl group (for example, trifluoromethyl) can be mentioned.

Hammett substituent constant σp As an electron-withdrawing group having a value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a halogenated alkoxy group (for example, , Trifluoromethyloxy), halogenated aryloxy group (eg, pentafluorophenyloxy), sulfonyloxy group (eg, methylsulfonyloxy group), halogenated alkylthio group (eg, difluoromethylthio), two or more σp values Is substituted with an electron withdrawing group of 0.15 or more (for example, 2,4-dinitrophenyl, pentachlorophenyl), and a heterocycle (for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl- 2-benzimidazolyl).

Hammett substituent constant σp Specific examples of the electron-withdrawing group having a value of 0.20 or more include a halogen atom in addition to the above.

As Z ₄ , among others, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. An arylsulfonyl group, a carbamoyl group having 1 to 20 carbon atoms, and a halogenated alkyl group having 1 to 20 carbon atoms are preferable. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

R ₄₁ , R ₄₂ , R ₄₅ and R ₄₆ in the general formula (4-D) have the same meaning as in the general formula (4-A). R ₄₃ and R ₄₄ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group. Represents. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group is preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable.

Each group described in the general formula (4-D) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (4-A), the groups exemplified for G ₄ , R ₄₁ and R ₄₂ , and ionic hydrophilic groups. Can be mentioned.

A particularly preferred combination of substituents as the azo dye represented by the general formula (4-B) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ₄₅ and R _46. And more preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group, and most preferably a hydrogen atom, an aryl group or a heterocyclic group. However, R ₄₅ and R ₄₆ are not both hydrogen atoms.
G ₄ is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an acylamino group, more preferably a hydrogen atom, a halogen atom, an amino group or an acylamino group, most preferably a hydrogen atom, An amino group and an acylamino group.
Of A _41, a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, and a benzothiazole ring are preferable, a pyrazole ring and an isothiazole ring are further preferable, and a pyrazole ring is most preferable.
B ₄₂ and B ₄₃ are ═CR ₄₁ — and —CR ₄₂ ═, respectively, and R ₄₁ and R ₄₂ are preferably hydrogen atom, alkyl group, halogen atom, cyano group, carbamoyl group, carboxyl group, hydroxyl group, respectively. , An alkoxy group and an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group and a carbamoyl group.

  As for the preferred combination of substituents of the azo dye, a compound in which at least one of various substituents is the preferred group is preferred, and a compound in which more various substituents are the preferred groups is more preferred, Most preferred are compounds in which all substituents are the preferred groups.

  Specific examples of the azo dye represented by the general formula (4) are shown below, but the present invention is not limited to the following examples, and among the following specific examples, a carboxyl group, a phosphono group, and a sulfo group. The group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (eg, tetramethylammonium ion). , Tetramethylguanidinium ion, tetramethylphosphonium), among which lithium ion is preferable.

  The azo dyes represented by the general formulas (4), (4-A), (4-B), and (4-D) can be synthesized by a coupling reaction between a diazo component and a coupler. As a main synthesis method, it can be synthesized by the method described in Japanese Patent Application No. 2002-113460.

  As the dye (S) having λmax of 350 nm to 500 nm, a yellow dye and a yellow pigment described later can be preferably used.

  The content of the azo dye represented by the general formula (4) in the ink is preferably 0.2 to 20% by mass, and more preferably 0.5 to 15% by mass.

  The ink of the present invention may be used in combination with other dyes in order to obtain a full-color image together with the dye or to adjust the color tone. The following can be mentioned as an example of the dye which can be used together.

  Examples of yellow dyes include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, open-chain active methylene compounds as coupling components. Azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species such as quinophthalone dyes, nitro-nitroso dyes And dyes, acridine dyes, acridinone dyes and the like. These dyes may be those that exhibit yellow only after a part of the chromophore is dissociated, in which case the counter cation may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

  Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components; azomethine dyes having pyrazolones and pyrazolotriazoles as coupling components; for example, arylidene dyes, styryl dyes, and merocyanine Dyes, methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc. And ring dyes. These dyes may exhibit magenta only after part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.

Examples of cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine Dyes; anthraquinone dyes; For example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes can be mentioned. These dyes may exhibit cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, and further may be a polymer cation having them in a partial structure.
Also, black dyes such as polyazo dyes can be used.

In addition, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes can be used in combination. Among them, preferred is
CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207 , 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247
CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101
CI Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100 , 106, 108, 109, 110, 130, 132, 142, 144, 161, 163
CI Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158 , 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251 252 264 270 280 288 289 291
CI Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132 , 146, 154, 166, 168, 173, 199
CI Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266 , 289, 299, 301, 305, 336, 337, 361, 396, 397
CI Acid Violet 5, 34, 43, 47, 48, 90, 103, 126
CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 , 196, 197, 199, 218, 219, 222, 227
CI Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326
CI Acid Black 7, 24, 29, 48, 52: 1, 172
CI Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55
CI Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34
CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42
CI Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38
CI Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34
CI Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46
CI Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48
CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40
CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71
CI Basic Black 8, etc.

Furthermore, a pigment can be used in combination.
As the pigment that can be used in the ink of the present invention, commercially available pigments and known pigments described in various documents can be used. Regarding the literature, the Color Index (Edited by The Society of Dyers and Colorists), “Revised New Handbook of Pigments” edited by the Japan Pigment Technology Association (published in 1989), “Latest Pigment Applied Technology” published by CMC (published in 1986), “Printing Ink Technology” CMC Publication (1984), Industrial Organic Pigments (VCH Verlagsgesellschaft, 1993) by W. Herbst and K. Hunger. Specifically, as organic pigments, azo pigments (azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, quinacridone Pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments), dyed lake pigments (acid or basic dye lake pigments), azine pigments, etc. CI Pigment Yellow 34, 37, 42, 53 for yellow pigments, CI Pigment Red 101, 108 for red pigments, CI Pigment Blue 27, 29, 17: 1 for blue pigments, CI Pigment Black for black pigments 7, CI Pigment White 4, 6, 18, 21, etc. of white pigments such as magnetite.

  As a pigment having a preferable color tone for image formation, a phthalocyanine pigment, an anthraquinone-based indanthrone pigment (for example, CI Pigment Blue 60), a dyed lake pigment-based triarylcarbonium pigment are preferable for blue to cyan pigments, and in particular phthalocyanine. Pigments (preferred examples include copper phthalocyanine such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, and 15: 6, monochloro or low chlorinated copper phthalocyanine, and arnium phthalocyanine. Pigment described in European Patent No. 860475, metal-free phthalocyanine which is CI Pigment Blue 16, phthalocyanine whose central metal is Zn, Ni, Ti, etc., among which CI Pigment Blue 15: 3, 15: 4, aluminum phthalocyanine ) Is most preferred.

  For red to violet pigments, azo pigments (preferred examples include CI Pigment Red 3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 3, 48: 3, 48: 3). 4, 49: 1, 52: 1, 53: 1, 57: 1, 63: 2, 144, 146, 184), etc. 146, 184), quinacridone pigments (preferred examples include CI Pigment Red 122, 192, 202, 207, 209, CI Pigment Violet 19, 42, and among them, CI Pigment Red 122). Dye-attached lake pigment triarylcarbonium pigments (preferred examples include xanthene CI Pigment Red 81: 1, CI Pigment Violet 1, 2, 3, 27, 39), dioxazine pigments (for example, CI Pigment Violet 23, 37), diketopyrrolopyrrole pigment (eg CI Pigment Red 254), perylene pigment (eg CI Pigment Violet 29), anthraquinone Fee (e.g., C. I. Pigment Violet 5: 1, the 31, the 33), thioindigo (e.g. C. I. Pigment Red 38, the 88) is preferably used.

  As yellow pigments, azo pigments (preferred examples include monoazo pigment-based CI Pigment Yellow 1, 3, 74, 98, disazo pigment-based CI Pigment Yellow 12, 13, 14, 16, 17, 83, CI Pigment Yellow 93, 94, 95, 128, 155, benzimidazolone CI Pigment Yellow 120, 151, 154, 156, 180, etc. Among them, preferred are those using benzidine compounds as raw materials), isoindoline Isoindolinone pigments (preferred examples include CI Pigment Yellow 109, 110, 137, 139), quinophthalone pigments (preferred examples include CI Pigment Yellow 138), and furapantron pigments (for example, CI Pigment Yellow 24) Preferably used.

Preferred examples of the black pigment include inorganic pigments (preferably carbon black and magnetite as examples) and aniline black.
In addition, an orange pigment (CI Pigment Orange 13, 16, etc.) or a green pigment (CI Pigment Green 7, etc.) may be used.

The pigment that can be used in the ink of the present invention may be the aforementioned bare pigment or a surface-treated pigment. Surface treatment methods include resin or wax surface coating, surfactant attachment, reactive substances (eg radicals derived from silane coupling agents, epoxy compounds, polyisocyanates, diazonium salts, etc.) pigments A method of bonding to the surface is conceivable, and is described in the following documents and patents.
(i) Properties and applications of metal soap (Sachishobo)
(ii) Printing ink printing (CMC Publishing 1984)
(iii) Latest pigment application technology (CMC Publishing 1986)
(iv) U.S. Patent Nos. 5,554,739 and 5,571,311
(v) JP-A-9-151342, JP-A-10-140065, JP-A-10-292143, JP-A-11-166145 In particular, prepared by reacting carbon black with the diazonium salt described in the above-mentioned US patent (iv) Self-dispersing pigments and encapsulated pigments prepared by the method described in the Japanese patent (v) above are particularly effective because dispersion stability can be obtained without using an extra dispersant in the ink. It is.

In the ink of the present invention, the pigment may be further dispersed using a dispersant. Various known dispersants can be used in accordance with the pigment to be used, for example, a surfactant-type low-molecular dispersant or a polymer-type dispersant. Examples of the dispersant include those described in JP-A-3-69949, European Patent 549486 and the like. In addition, when a dispersant is used, a pigment derivative called a synergist may be added to promote adsorption of the dispersant to the pigment.
The particle size of the pigment that can be used in the ink of the present invention is preferably in the range of 0.01 to 10 μm after dispersion, and more preferably 0.05 to 1 μm.
As a method for dispersing the pigment, a known dispersion technique used in ink production or toner production can be used. Examples of the disperser include vertical or horizontal agitator mills, attritors, colloid mills, ball mills, three roll mills, pearl mills, super mills, impellers, dispersers, KD mills, dynatrons, and pressure kneaders. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

  The ink used in the ink set of the present invention can be prepared by dissolving or dispersing the dye and preferably a surfactant in an aqueous medium. The “aqueous medium” in the present invention means a mixture of water and the water-miscible organic solvent with additives such as stabilizers and preservatives added as necessary.

When preparing the ink liquid of the present invention, in the case of water-soluble ink, it is preferable to first dissolve in water. Thereafter, various solvents and additives are added, dissolved and mixed to obtain a uniform ink solution.
As the dissolution method at this time, various methods such as dissolution by stirring, dissolution by ultrasonic irradiation, and dissolution by shaking can be used. Of these, the stirring method is particularly preferably used. In the case of stirring, various methods such as fluidized stirring known in the art and stirring using shearing force using an inverted agitator or dissolver can be used. On the other hand, a stirring method using a shearing force with the bottom surface of the container, such as a magnetic stirrer, can also be preferably used.

When the dye is an oil-soluble dye, it can be prepared by dissolving the oil-soluble dye in a high-boiling organic solvent and emulsifying and dispersing it in an aqueous medium.
The boiling point of the high-boiling organic solvent used in the present invention is 150 ° C. or higher, preferably 170 ° C. or higher.
For example, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1, 1-diethylpropyl) phthalate), esters of phosphoric acid or phosphones (eg diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate , Tridodecyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (eg 2-ethylhexyl benzoate, 2,4-dicarbonate) Lobenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecanamide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2, 4-di-tert-amylphenol), aliphatic esters (eg, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate , Trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters Kind (for example, Tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl)) Phenol), carboxylic acids (eg, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid) The high-boiling organic solvent can be used in an amount of 0.01 to 3 times, preferably 0.01 to 1.0 times the mass ratio of the oil-soluble dye.
These high-boiling organic solvents may be used alone or in a mixture of several types (eg tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and poly (Nt-butyl). Acrylamide)].

Examples of other high boiling point organic solvents used in the present invention and / or methods for synthesizing these high boiling point organic solvents are disclosed in, for example, US Pat. Nos. 2,322,027, 2,533,514, and 2 772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4, No. 004,928, No. 4,080,209, No. 4,127,413, No. 4,193,802, No. 4,207,393, No. 4,220,711, No. 4,239,851, No. 4,278,757, No. 4 353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606, 4,728,599, 4,745,049, 4,935,321, 5,013 , 639, European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509 No. 311A, No. 510,576A, East German Patent No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A, JP-A-48-47335, 50 No. 26530, No. 51-25133, No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149028, No. 52-46816, No. 53-1520, No. 53-1521 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84641, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 63-94552, 64-945 9454, 64-68745, JP-A-1-101543, 1-102454, 2-792, and 2 No.-4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338 and the like.
The high boiling point organic solvent is used in an amount of 0.01 to 3.0 times, preferably 0.01 to 1.0 times the mass ratio of the oil-soluble dye.

  In the present invention, the oil-soluble dye and the high boiling point organic solvent are emulsified and dispersed in an aqueous medium. In the emulsification dispersion, a low boiling organic solvent can be used depending on the case from the viewpoint of emulsification. The low boiling point organic solvent is an organic solvent having a boiling point of about 30 ° C. or higher and 150 ° C. or lower at normal pressure. For example, esters (eg ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (eg isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (eg methyl isobutyl) Ketones, methyl ethyl ketone, cyclohexanone), amides (for example, dimethylformamide, N-methylpyrrolidone), ethers (for example, tetrahydrofuran, dioxane) and the like are preferably used, but are not limited thereto.

The emulsification dispersion is used to disperse an oil phase in which a dye is dissolved in a mixed solvent of a high-boiling organic solvent and, optionally, a low-boiling organic solvent, in an aqueous phase mainly composed of water to form fine oil droplets in the oil phase. Done. At this time, additives such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, an antiseptic and an antifungal agent, which will be described later, are added to either or both of the aqueous phase and the oil phase as necessary. be able to.
As an emulsification method, a method of adding an oil phase to an aqueous phase is common, but a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used. The emulsification method can also be applied when the dye used in the present invention is water-soluble and the additive is oil-soluble.

When emulsifying and dispersing, various surfactants can be used. Anionic interfaces such as fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfate esters, etc. Activator, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethyleneoxypropylene block copolymer Nonionic surfactants such as
Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used.

For the purpose of stabilization immediately after emulsification, a water-soluble polymer can be added in combination with the surfactant. As the water-soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide or a copolymer thereof is preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein, and gelatin. Further, for stabilization of the dye dispersion, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers that are not substantially soluble in an aqueous medium, Polyvinyl, polyurethane, polyester, polyamide, polyurea, polycarbonate and the like obtained by polymerization of acrylonitrile can also be used in combination. These polymers preferably contain —SO ₃ ⁻ and —COO ⁻ . When these polymers that do not substantially dissolve in an aqueous medium are used in combination, it is preferably used in an amount of 20% by mass or less, more preferably 10% by mass or less of the high boiling point organic solvent.

When an oil-soluble dye or a high-boiling organic solvent is dispersed by emulsification to obtain a water-based ink, control of the particle size is particularly important. In order to increase color purity and density when an image is formed by inkjet, it is essential to reduce the average particle size. The volume average particle size is preferably 1 μm or less, more preferably 5 to 100 nm.
In addition to static light scattering, dynamic light scattering, and centrifugal sedimentation, the methods for measuring the volume average particle size and particle size distribution of the dispersed particles are described in pages 417 to 418 of Experimental Chemistry Course 4th edition. It can be easily measured by a known method such as using a method.
For example, after dilution with distilled water so that the particle concentration in the ink is 0.1 to 1% by mass, it is easy with a commercially available volume average particle size measuring device (for example, Microtrac UPA (manufactured by Nikkiso Co., Ltd.)). Can be measured. Furthermore, the dynamic light scattering method using the laser Doppler effect is particularly preferable because it can measure the particle size up to a small size.
The volume average particle diameter is an average particle diameter weighted by the particle volume, and is the sum of the diameter of each particle multiplied by the volume of the particle divided by the total volume of the particles. The volume average particle diameter is described on page 119 of “Chemistry of Polymer Latex (by Soichi Muroi, Polymer Press Society)”.

It was also found that the presence of coarse particles also plays a very important role in printing performance. That is, it has been found that the coarse particles clog the nozzles of the head, or even if they are not clogged, the ink is not ejected or the ink is not ejected, resulting in a serious influence on the printing performance. In order to prevent this, it is important to limit the number of particles of 5 μm or more to 10 or less and 1 μm or more to 1000 or less in 1 μl of ink.
As a method for removing these coarse particles, a known centrifugal separation method, microfiltration method, or the like can be used. These separation means may be performed immediately after the emulsification dispersion, or may be performed immediately after filling the ink dispersion with various additives such as a wetting agent and a surfactant.
A mechanical emulsifier can be used as an effective means for reducing the average particle size and eliminating coarse particles.

As the emulsifying device, known devices such as a simple stirrer, impeller stirring method, in-line stirring method, mill method such as colloid mill, and ultrasonic method can be used, but the use of a high-pressure homogenizer is particularly preferable.
As for the high-pressure homogenizer, detailed mechanisms are described in US Pat. No. 4,533,254, JP-A-6-47264, and the like. MICROFLUIDEX INC.), Optimizer (Sugino Machine Co., Ltd.) and the like.
In addition, a high-pressure homogenizer equipped with a mechanism for making fine particles in an ultrahigh-pressure jet stream as described in US Pat. An example of an emulsifying apparatus using this ultra-high pressure jet flow is DeBEE2000 (BEE INTERNIONAL LTD.).

The pressure when emulsifying with the high-pressure emulsifying dispersion device is 50 MPa or more, preferably 60 MPa or more, more preferably 180 MPa or more.
For example, it is a particularly preferable method that two or more types of emulsifiers are used together by a method such as emulsification with a stirring emulsifier and then passing through a high-pressure homogenizer. Also preferred is a method of once emulsifying and dispersing with these emulsifiers, adding an additive such as a wetting agent or a surfactant, and then passing the high-pressure homogenizer again while filling the cartridge with ink.
When a low boiling point organic solvent is contained in addition to the high boiling point organic solvent, it is preferable to remove the low boiling point solvent from the viewpoint of the stability of the emulsion and safety and health. Various known methods can be used as the method for removing the low boiling point solvent depending on the type of the solvent. That is, an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like. This step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

  Ink jet ink preparation methods are described in detail in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Thus, it can also be used for preparing the ink for inkjet recording of the present invention.

In the production of the ink-jet ink of the present invention, ultrasonic vibration can be applied to the dissolution process of additives such as dyes.
Ultrasonic vibration is a bubble created by applying ultrasonic energy equal to or higher than the energy received by the recording head in advance during the ink manufacturing process in order to prevent ink from generating bubbles due to the pressure applied by the recording head. Is to be removed.
The ultrasonic vibration is usually an ultrasonic wave having a frequency of 20 kHz or higher, preferably 40 kHz or higher, more preferably 50 kHz. The energy applied to the liquid by ultrasonic vibration is usually 2 × 10 ⁷ J / m ³ or more, preferably 5 × 10 ⁷ J / m ³ or more, more preferably 1 × 10 ⁸ J / m ³ or more. . Moreover, the application time of ultrasonic vibration is usually about 10 minutes to 1 hour.

The step of applying ultrasonic vibration shows an effect at any time after the dye is put into the medium. The effect is exhibited even if ultrasonic vibration is applied after the completed ink is once stored. However, adding ultrasonic vibration when the dye is dissolved and / or dispersed in the medium has a greater effect of removing bubbles, and the ultrasonic vibration promotes dissolution and / or dispersion of the dye in the medium. This is preferable.
That is, the step of applying at least ultrasonic vibration can be performed in any case, either during or after the step of dissolving and / or dispersing the dye in the medium. In other words, the step of applying at least the ultrasonic vibration can be arbitrarily performed once or more after the ink preparation until it becomes a product.

As an embodiment, the step of dissolving and / or dispersing in the medium preferably includes a step of dissolving the dye in a medium of a part of the entire medium and a step of mixing the remaining medium, and at least one of the above It is preferable to apply ultrasonic vibration to this step, and it is more preferable to apply at least ultrasonic vibration to the step of dissolving the dye in a part of the medium.
The step of mixing the remaining solvent may be a single step or a plurality of steps.

In addition, it is preferable to use heat degassing or vacuum degassing in combination with the ink production according to the present invention because the effect of removing bubbles in the ink is improved. The heating degassing step or the vacuum degassing step is preferably performed simultaneously with or after the step of mixing the remaining medium.
Examples of the ultrasonic vibration generating means in the step of applying ultrasonic vibration include known devices such as an ultrasonic disperser.

  When producing the ink-jet ink of the present invention, a step of removing dust that is a solid content by filtration, which is carried out after further preparation, is important. A filtration filter is used for this work. The filtration filter at this time is a filter having an effective diameter of 1 μm or less, preferably 0.3 μm or less and 0.05 μm or more, particularly preferably 0.3 μm or less and 0.25 μm or more. Use. Various materials can be used as the filter material, but in the case of water-soluble dye inks, it is preferable to use a filter prepared for an aqueous solvent. Among them, it is particularly preferable to use a filter made of a polymer material that hardly generates dust. As the filtration method, the solution may be passed through a solution, and either pressure filtration or vacuum filtration can be used.

  After this filtration, air is often taken into the solution. Since bubbles caused by air often cause image disturbance in ink jet recording, it is preferable to separately provide the aforementioned defoaming step. As the defoaming method, the filtered solution may be allowed to stand, or various methods such as ultrasonic defoaming and vacuum defoaming using a commercially available apparatus can be used. In the case of defoaming with ultrasonic waves, the defoaming operation is preferably performed for about 30 seconds to 2 hours, more preferably about 5 minutes to 1 hour.

  These operations are preferably performed using a space such as a clean room or a clean bench in order to prevent dust from entering during the operation. In the present invention, it is particularly preferable to perform this operation in a space of class 1000 or less as the degree of cleanliness. Here, “cleanness” refers to a value measured by a dust counter.

  The ink-jet ink of the present invention includes a drying inhibitor for preventing clogging due to dry operation at the ink ejection port, a penetration accelerator for allowing the ink to penetrate better into the paper, an ultraviolet absorber, an antioxidant, An appropriate amount of additives such as a viscosity modifier, a surface tension modifier, a dispersant, a dispersion stabilizer, an antifungal agent, a rust inhibitor, a pH adjuster, and an antifoaming agent can be appropriately selected and used.

  The drying inhibitor used in the present invention is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether , Heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said drying inhibitor may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  Examples of penetration enhancers used in the present invention include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. Etc. can be used. If these are contained in the ink in an amount of 10 to 30% by mass, they are sufficiently effective, and it is preferable to use them in a range of addition amounts that do not cause bleed of prints and paper loss (print through).

  Examples of the ultraviolet absorber used for improving the storability of the image in the present invention include JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194443, US Pat. No. 3,214,463, etc. 48-30492, 56-21114, and cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, and 8-239368. Triazine compounds and research discs described in JP-A-10-182621, JP-A-8-501291, etc. Ja No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based compounds and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  In the present invention, various organic and metal complex anti-fading agents can be used as the antioxidant used to improve image storage stability. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII I to J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

Antifungal agents used in the present invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and its salts. Can be mentioned. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.
Details of these are described in “Encyclopedia of Antibacterial and Antifungal Agents” (edited by the Japanese Association of Antimicrobial and Antifungal Society).
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole. These are preferably used in the ink in an amount of 0.02 to 5.00% by mass.

The pH adjuster used in the present invention can be suitably used in terms of adjusting pH, imparting dispersion stability, etc., and the pH of the ink at 25 ° C. is preferably adjusted to 8-11. When the pH is less than 8, the solubility of the dye is lowered and the nozzle is easily clogged, and when it exceeds 11, the water resistance tends to deteriorate. Examples of the pH adjuster include organic bases and inorganic alkalis as basic substances, and organic acids and inorganic acids as acidic substances.
Basic compounds include inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium phosphate, sodium hydrogen phosphate, aqueous ammonia, Use organic bases such as methylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, piperidine, diazabicyclooctane, diazabicycloundecene, pyridine, quinoline, picoline, lutidine, collidine Is also possible.
Examples of acidic compounds include inorganic compounds such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sodium hydrogen sulfate, potassium hydrogen sulfate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, acetic acid, tartaric acid, benzoic acid, trifluoroacetic acid. Organic compounds such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, saccharic acid, phthalic acid, picolinic acid and quinolinic acid can also be used.

The conductivity of the ink of the present invention is in the range of 0.01 to 10 S / m. Among these, a preferable range is a conductivity of 0.05 to 5 S / m.
The conductivity can be measured by an electrode method using commercially available saturated potassium chloride.
The conductivity can be controlled mainly by the ion concentration in the aqueous solution. When the salt concentration is high, desalting can be performed using an ultrafiltration membrane or the like. Moreover, when adjusting conductivity by adding salt etc., it can adjust by adding various organic substance salt and inorganic substance salt.
Inorganic salts include potassium halide, sodium halide, sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium nitrate, potassium nitrate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium monohydrogen phosphate, Inorganic compounds such as boric acid, potassium dihydrogen phosphate, sodium dihydrogen phosphate, sodium acetate, potassium acetate, potassium tartrate, sodium tartrate, sodium benzoate, potassium benzoate, sodium p-toluenesulfonate, potassium saccharinate Organic compounds such as potassium phthalate and sodium picolinate can also be used.
The conductivity can also be adjusted by selecting other additive components.

The ink viscosity of the present invention is 1 to 20 mPa · s at 25 ° C. More preferably, it is 2-15 mPa * s, Most preferably, it is 2-10 mPa * s. If it exceeds 30 mPa · s, the fixing speed of the recorded image becomes slow, and the discharge performance also deteriorates. If it is less than 1 mPa · s, the recorded image is blurred and the quality is lowered.
The viscosity can be arbitrarily adjusted by adding the ink solvent. Examples of the ink solvent include glycerin, diethylene glycol, triethanolamine, 2-pyrrolidone, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether.
A viscosity modifier may be used. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants. For more details, see Chapter 9 of “Viscosity Preparation Technology” (Technical Information Association, 1999), and “Chemicals for Inkjet Printers (98 Supplement)-Material Development Trends and Perspective Survey” (CMC, 1997) 162- Page 174.

  The method for measuring the viscosity of the liquid is described in detail in JIS Z8803, but can be easily measured with a commercially available viscometer. For example, the rotary type includes Tokyo Keiki B-type viscometer and E-type viscometer. In this invention, it measured at 25 degreeC by the vibration type VM-100AL type of Yamaichi Electric. The unit of viscosity is Pascal second (Pa · s), but millipascal second (mPa · s) is usually used.

The static surface tension of the ink used in the present invention is preferably 20 to 50 mNm or less at 25 ° C., more preferably 20 to 40 mNm or less. When the static surface tension exceeds 50 mNm, the ejection stability, the bleeding at the time of color mixing, and the print quality such as whiskers are remarkably deteriorated. Further, when the static surface tension of the ink is set to 20 mNm or less, there may be a case where printing failure occurs due to adhesion of ink to the hard surface during ejection. The static surface tension is adjusted by the type and amount of the surfactant as in the case of the dynamic surface tension.
As a static surface tension measuring method, a capillary rising method, a dropping method, a hanging ring method and the like are known. In the present invention, a vertical plate method is used as a static surface tension measuring method.
When a thin plate of glass or platinum is partially immersed in the liquid and suspended vertically, the surface tension of the liquid acts downward along the portion where the liquid surface and the plate are in contact. The surface tension can be measured by balancing this force with an upward force.

The non-volatile component in the ink of the present invention is 10 to 70% by mass of the total amount of the ink. Ink ejection stability, print image quality, various image robustness, image bleeding after printing, and stickiness of the printing surface In terms of reduction, it is preferably 20 to 60% by mass, and more preferably in terms of ink ejection stability and reduction of image blur after printing.
Here, the non-volatile component means a liquid, a solid component or a high molecular weight component having a boiling point of 150 ° C. or higher under 1 atm. Non-volatile components of ink for ink-jet recording are dyes, high-boiling solvents, polymer latex added if necessary, surfactants, dye stabilizers, antifungal agents, buffering agents, etc. Other than the dye stabilizer, the dispersion stability of the ink is lowered, and since it remains on the inkjet image-receiving paper after printing, the stabilization due to the association of the dye on the image-receiving paper is inhibited, and various fastnesses and It has the property of exacerbating image bleeding under humidity conditions.

  In the present invention, a high molecular weight compound can also be contained. Here, the high molecular weight compound means all high molecular compounds having a number average molecular weight of 5000 or more contained in the ink. These polymer compounds are soluble in water-soluble polymer compounds that are substantially soluble in aqueous media, water-dispersible polymer compounds such as polymer latex and polymer emulsion, and polyhydric alcohols that are used as auxiliary solvents. Alcohol-soluble polymer compounds and the like can be mentioned, but any compound that substantially dissolves or disperses uniformly in the ink liquid is included in the high molecular weight compound in the present invention.

Specific examples of water-soluble polymer compounds include polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyethylene oxide, water-soluble polymers such as polyoxyalkylene oxide such as polypropylene oxide, polyalkylene oxide derivatives, polysaccharides, starch, cationized starch, casein, natural water-soluble polymers such as gelatin, polyacrylic acid, polyacrylamide or aqueous acrylic resins such as a copolymer thereof, aqueous alkyd resins, -SO in the molecule ₃ ^-, Examples thereof include water-soluble polymer compounds having a —COO 2 ^— group which are substantially soluble in an aqueous medium.
Examples of the polymer latex include styrene butadiene latex, styrene-acrylic latex, and polyurethane latex. Furthermore, an acrylic emulsion etc. are mentioned as a polymer emulsion.
These water-soluble polymer compounds can be used alone or in combination of two or more.

As described above, the water-soluble polymer compound is used as a viscosity modifier to adjust the viscosity of the ink in a viscosity region having good ejection characteristics. However, if the amount of the water-soluble polymer compound added is large, the viscosity of the ink increases. As a result, the ejection stability of the ink liquid is lowered, and the nozzle is easily clogged by the precipitate when the ink is aged.
The addition amount of the polymer compound of the viscosity modifier depends on the molecular weight of the compound to be added (the higher the molecular weight, the smaller the addition amount may be), but the addition amount is 0 to 5% by mass with respect to the total amount of the ink, preferably Is 0 to 3% by mass, more preferably 0 to 1% by mass.
In the present invention, nonionic, cationic or anionic surfactants may be mentioned as surface tension adjusting agents in addition to the surfactants described above. For example, anionic surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylamines, glycerin fatty acid esters, and oxyethyleneoxypropylene block copolymers. SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  Further, in the present invention, the above-mentioned cation, anion, and nonionic surfactants are used as a dispersant and a dispersion stabilizer, and fluorine-based, silicone-based compounds, and chelating agents represented by EDTA are used as necessary as an antifoaming agent. can do.

[Recording material]
Examples of the recording material used in the present invention include recording paper and recording film, which are reflective media described below. The recording material of the present invention includes an ink receiving layer containing a betaine compound (preferably on a support). Provided).

The support for recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. As the support, in addition to these supports, either synthetic paper or plastic film sheet may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m ² .
An ink receiving layer and a backcoat layer may be provided on the support as they are to provide a recording material for the ink of the present invention, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, the ink receiving layer and the backcoat layer May be used as a recording material. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
In the present invention, as the support, paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polybutene and copolymers thereof) or polyethylene terephthalate are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a porous material and an aqueous binder. The ink receiving layer preferably contains a pigment, and the pigment is preferably a white pigment. White pigments 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, titanium dioxide, Examples thereof include inorganic white pigments such as zinc sulfide and zinc carbonate, organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. A porous white inorganic pigment is particularly preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method (gas phase method) or hydrous silicic acid obtained by a wet production method can be used.

  Specific examples of the recording paper containing the pigment in the ink receiving layer include JP-A Nos. 10-81064, 10-119423, 10-157277, 10-217601, and 11-348409. JP-A-2001-138621, JP-A-2000-43401, JP-A-2000-21235, JP-A-2000-309157, JP-A-2001-96897, JP-A-2001-138627, JP-A-11-91242, JP-A-8-2087, Those disclosed in JP-A-8-2090, JP-A-8-2091, JP-A-8-2093, JP-A-8-174992, JP-A-11-192777, JP-A-2001-301314 and the like can be used.

  Examples of the aqueous binder contained in the ink receiving layer include water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, and the like. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.

  The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a gas resistance improver, a surfactant, a hardener and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305, It is described in each specification of the same No. 4450224. A recording material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, and cationic polyacrylamide. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

Examples of the light resistance improver and gas resistance improver include phenol compounds, hindered phenol compounds, thioether compounds, thiourea compounds, thiocyanate compounds, amine compounds, hindered amine compounds, TEMPO compounds, hydrazine compounds, hydrazide compounds, amidine compounds, Vinyl group-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinic acid compounds, saccharides, water-soluble reducing compounds, organic acids, inorganic acids, hydroxy group-containing organic acids, benzotriazole compounds, benzophenone compounds, triazine compounds , Heterocyclic compounds, water-soluble metal salts, organometallic compounds, metal complexes and the like.
Specific examples of these compounds include JP-A-10-182621, JP-A-2001-260519, JP-A-2000-260519, JP-B-4-34953, JP-B-4-34513, and JP-B-4-34512. , JP-A-11-170686, JP-A-60-67190, JP-A-7-276808, JP-A-2000-94829, JP-T 8-512258, JP-A-11-321090, etc. Can be given.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457.
An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (eg, fluorine oil), and a solid fluorine compound resin (eg, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826.

  As the hardener, materials described in JP-A-1-161236, page 222, JP-A-9-263036, JP-A-10-119423, and JP-A-2001-310547 can be used.

  Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components.
Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, white inorganic pigment, styrene And organic pigments such as polyethylene plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

  A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the inkjet recording paper and recording film. The polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer fine particle dispersion is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer fine particle dispersion having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Further, even when a polymer fine particle dispersion having a high glass transition temperature is added to the back layer, curling can be prevented.

[Inkjet recording method]
The ink jet recording method of the present invention uses a betaine compound-containing ink and a recording material having a betaine compound-containing ink receiving layer. The betaine compound used in the ink is preferably a compound represented by the general formula (B1) or (B2), and the betaine compound used in the ink receiving layer is preferably a sulfobetaine compound.

In the present invention, there is no limitation on the ink jet recording method, and a known method, for example, a charge control method for ejecting ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element, and the like. ), An acoustic ink jet system that converts electrical signals into acoustic beams, irradiates the ink and ejects ink using radiation pressure, and thermal ink jet (bubble jet) that uses the pressure generated by heating the ink to form bubbles ) Method.
Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included. The ink droplet volume is controlled mainly by the print head.

For example, in the case of the thermal ink jet method, the droplet ejection volume can be controlled by the structure of the print head. That is, droplets can be ejected in a desired size by changing the sizes of the ink chamber, the heating unit, and the nozzle. Even in the case of the thermal ink jet method, it is possible to realize droplet ejection of a plurality of sizes by providing a plurality of print heads having different heating parts and nozzle sizes.
In the case of the drop-on-demand method using a piezo element, the droplet ejection volume can be changed due to the structure of the print head as in the thermal ink jet method, but the waveform of the drive signal that drives the piezo element is controlled as described later. By doing so, droplets of a plurality of sizes can be ejected with a print head having the same structure.

In the inkjet ink of the present invention, the average droplet ejection speed when ejecting onto a recording material is preferably 2 m / sec or more, and more preferably 5 m / sec or more.
The droplet ejection speed is controlled by controlling the shape and amplitude of the waveform that drives the head.
In addition, by using a plurality of drive waveforms properly, it is possible to eject droplets of a plurality of sizes with the same head.

  The inkjet ink of the present invention can also be used for applications other than inkjet recording. For example, it can be used for display image materials, image forming materials for interior decoration materials, and image forming materials for outdoor decoration materials.

[Example]
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is of course not limited to the examples.

After adding ultrapure water having a resistance value of 18 MΩ or more to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Thereafter, the ink liquid of each color was prepared by filtering under reduced pressure through a microfilter having an average pore diameter of 0.25 μm.
[Light cyan ink formulation]
(Solid content)
Cyan dye (C-1) 20g / l
Urea (UR) 15g / l
Benzotriazole (BTZ) 0.08g / l
PROXEL XL2 (PXL) 3.5g / l
(Liquid component)
Triethylene glycol (TEG) 110g / l
Glycerin (GR) 130g / l
Triethylene glycol monobutyl ether (TGB) 110g / l
2-pyrrolidone (PRD) 60g / l
Triethanolamine (TEA) 7g / l
Surfynol STG (SW) 10g / l

[Cyan ink prescription]
(Solid content)
Cyan dye (C-1) 60g / l
Urea (UR) 30g / l
Benzotriazole (BTZ) 0.08g / l
PROXEL XL2 (PXL) 3.5g / l
(Liquid component)
Triethylene glycol (TEG) 110g / l
Glycerin (GR) 130g / l
Triethylene glycol monobutyl ether (TGB) 130g / l
2-pyrrolidone (PRD) 60g / l
Triethanolamine (TEA) 7g / l
Surfynol STG (SW) 10g / l
[Light magenta ink prescription]
(Solid content)
Magenta dye (M-1) 10g / l
Urea (UR) 10g / l
Proxel 5g / l
(Liquid component)
Diethylene glycol (DEG) 100g / l
Glycerin (GR) 140g / l
Triethylene glycol monobutyl ether (TGB) 90g / l
Triethanolamine (TEA) 8g / l
Surfynol STG (SW) 10g / l
[Magenta ink prescription]
(Solid content)
Magenta dye (M-1) 33 g / l
Urea (UR) 15g / l
Proxel 5g / l
(Liquid component)
Diethylene glycol 90g / l
Glycerin 150g / l
Triethylene glycol monobutyl ether 100g / l
Triethanolamine 8g / l
Surfynol STG 10g / l

[Yellow ink prescription]
(Solid content)
Yellow dye (Y-1) 35g / l
Proxel 3.5g / l
Benzotriazole (BTZ) 0.08g / l
Urea 10g / l
(Liquid component)
Triethylene glycol monobutyl ether (TGB) 130g / l
Glycerin (GR) 135g / l
Diethylene glycol (DEG) 120g / l
2-pyrrolidone 35g / l
Triethanolamine (TEA) 8g / l
Surfynol STG (SW) 10g / l
[Dark yellow ink prescription]
(Solid content)
Yellow dye (Y-1) 35g / l
Magenta dye (M-1) 2g / l
Cyan dye (C-1) 2g / l
Proxel 5g / l
Benzotriazole (BTZ) 0.08g / l
Urea 10g / l
(Liquid component)
Triethylene glycol monobutyl ether (TGB) 140g / l
Glycerin (GR) 125g / l
Diethylene glycol (DEG) 120g / l
2-pyrrolidone 35g / l
Triethanolamine (TEA) 8g / l
Surfynol STG (SW) 10g / l

[Black ink prescription]
(Solid content)
Black dye (BK-1) 75g / l
Black dye (BK-2) 30g / l
Proxel 5g / l
Urea 10g / l
Benzotriazole 3g / l
(Liquid component)
Diethylene glycol monobutyl ether (DGB) 120g / l
Glycerin (GR) 125g / l
Diethylene glycol (DEG) 100g / l
2-pyrrolidone 35g / l
Triethanolamine (TEA) 8g / l
Surfynol STG (SW) 10g / l
An ink set composed of these inks was designated as IS-101. Ink sets IS-102 to 105 were made of the same inks except that the additives shown in the table below were added to the inks of this ink set. The oxidation potential of all the dyes of the invention used is greater than 1,2 V (vs SCE).

PEG: Polyethylene glycol (molecular weight 10000)
<Production of image receiving sheet>
(Preparation of coating liquid A for ink receiving layer)
[1] Gas phase method silica fine particles, [2] ion-exchanged water, and [3] “PAS-M-1” in the following composition are mixed, and using KD-P (manufactured by Shinmaru Enterprises Co., Ltd.) Then, after dispersing for 20 minutes at a rotational speed of 10,000 rpm, a solution containing the following [4] polyvinyl alcohol, [5] boric acid, [6] polyoxyethylene lauryl ether, and [7] ion-exchanged water is added, and the mixture is further rotated. Dispersion was again performed at several 10000 rpm for 20 minutes to prepare an ink-receiving layer coating solution A.
The mass ratio between the silica fine particles and the water-soluble resin (PB ratio = [1]: [4]) is 4.5: 1, and the pH of the coating liquid A for ink-receiving layer is 3.5, indicating acidity. It was.

<Composition of ink receiving layer coating liquid A>
[1] Gas phase method silica fine particles (inorganic fine particles) 10.0 parts ("Reoceal QS-30" manufactured by Tokuyama Corporation, average primary particle diameter 7 nm)
[2] 51.7 parts of ion exchange water
[3] "PAS-M-1" (60% aqueous solution) 0.83 parts (dispersant, manufactured by Nittobo Co., Ltd.)
[4] Polyvinyl alcohol (water-soluble resin) 8% aqueous solution 27.8 parts ("PVA124" manufactured by Kuraray Co., Ltd., saponification degree 98.5%, polymerization degree 2400)
[5] Boric acid (crosslinking agent) 0.4 parts
[6] 1.2 parts of polyoxyethylene lauryl ether (surfactant) (“Emulgen 109P” (10% aqueous solution) manufactured by Kao Corporation, HLB value 13.6)
[7] Ion exchange water 33.0 parts

(Preparation of inkjet recording material)
After the corona discharge treatment is applied to the front surface of the support, the coating liquid A for the ink receiving layer obtained above is applied to the front surface of the support at an application amount of 200 ml / m ² using an extrusion die coater. (Applying step), and dried with a hot air dryer at 80 ° C. (wind speed of 3 to 8 m / sec) until the solid content concentration of the coating layer reached 20%. This coating layer exhibited a constant rate of drying during this period. Immediately after that, it was immersed in a mordant solution B having the following composition for 30 seconds to deposit 20 g / m ² on the coating layer (step of applying a mordant solution), and further dried at 80 ° C. for 10 minutes (drying step). ). Thus, an inkjet recording material R-1 of the present invention provided with an ink receiving layer having a dry film thickness of 32 μm was produced.

<Composition of mordant coating liquid B>
[1] Boric acid (crosslinking agent) 0.65 parts
[2] 25% polyallylamine “PAA-10C” 10% aqueous solution (mordant, manufactured by Nittobo Co., Ltd.)
[3] 59.7 parts of ion exchange water
[4] Ammonium chloride (surface pH adjuster) 0.8 parts
[5] 10 parts of polyoxyethylene lauryl ether (surfactant) ("Emulgen 109P" manufactured by Kao Corporation, 2% aqueous solution, HLB value 13.6)
[6] MegaFac "F1405" 10% aqueous solution 2.0 parts (Fluorine surfactant manufactured by Dainippon Ink & Chemicals, Inc.)

  Inkjet recording sheets R-2 to R-8 having the same composition as R-1 were respectively prepared except that additives were added to the inkjet recording sheet R-1 as described below.

POEP-1: Polyoxyethylene nonylphenyl ether (PEO chain average 30)
POEN-1: Polyoxyethylene naphthyl ether (PEO chain average 50)
These inks were loaded into an ink cartridge of an ink-jet printer PM-980C manufactured by EPSON, and an image pattern in which the density changed stepwise for C, M, Y, B, G, and R6 colors and gray was printed.
The image receiving sheets used here were R-1 to R-8.
<Evaluation of light fastness>
After measuring the image density Ci immediately after printing with X-rite 310, after irradiating the image with xenon light (85,000 lux) for 30 days using an Atlas weather meter, the image density Cf was measured again and dyed. The residual rate Cf / Ci × 100 was obtained and evaluated. Dye afterimage rate For each single color of C, M, and Y, and the gray part, the reflection density is evaluated at three points of 1, 1.5, and 2, and the dye residual rate is 80% or more at any density , A when 1 or 2 points are less than 80%, B, and C when less than 80% at all concentrations.
<Evaluation of image blur>
For image bleeding under high-humidity conditions, the image sample printed on photo glossy paper was tested against the above-mentioned pattern image by storing it at 25 ° C. and 90% RH for 7 days.
The case where the bleeding of the dye was observed on the white background portion was marked with ×, and the case where the white background remained as an image was marked with ○.
<Evaluation of ozone fastness>
For ozone resistance, the photo glossy paper on which the image is formed is left in a box where the ozone gas concentration is set to 5 ppm for 7 days, and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR). It was measured using and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 80% or more at any concentration, A being 1 or 2 points being less than 80% B, and C being less than 70% at all concentrations.
The results are shown below.

  From the above results, the effect of the present invention is clear.

Claims (9)

  In an ink jet recording method for forming an image by ejecting ink droplets in accordance with image information onto an ink jet recording material having an ink receiving layer on a support, and forming the image on the ink receiving layer, the ink receiving layer is formed on the ink receiving layer. An inkjet recording method comprising a betaine compound.   2. The ink jet recording method according to claim 1, wherein the oxidation potential of at least one dye contained in the ink is 1.0 V or more.   3. The inkjet recording method according to item 1 or 2, wherein the ink receiving layer further contains a water-soluble resin.   The water-soluble resin is at least one of a polyvinyl alcohol resin, a cellulose resin, a resin having an ether bond, a resin having a carbamoyl group, a resin having a carboxyl group, and gelatins. The inkjet recording method according to any one of the items.   The inkjet recording method according to any one of Items 1 to 4, wherein the ink receiving layer further contains fine particles.   The inkjet recording method according to any one of Items 1 to 4, wherein the fine particles are at least one of silica fine particles, colloidal silica, alumina fine particles, and pseudoboehmite.   The inkjet recording method according to any one of Items 1 to 6, wherein the ink receiving layer further contains a crosslinking agent capable of crosslinking the water-soluble resin.   8. The ink jet recording method according to any one of items 1 to 7, wherein the ink receiving layer further contains a mordant. 9. The ink jet recording method according to any one of claims 1 to 8, wherein at least one dye represented by the following general formulas (1) to (4) is used as the dye of the ink.
General formula (1);
(A ₁₁ −N = N−B ₁₁ ) n ₁ -Ly
In the general formula (1), A ¹¹ and B ¹¹ each independently represents an optionally substituted heterocyclic group. n ₁ is 1 or 2, and Ly represents a hydrogen atom or a substituent bonded to A ₁₁ or B ₁₁ at an arbitrary position. Ly represents a hydrogen atom, a monovalent substituent, a simple bond, or a divalent linking group. However, when n ₁ is 1, Ly represents a hydrogen atom or a monovalent substituent, and both A ₁₁ and B ₁₁ are monovalent heterocyclic groups. When n ₁ is 2, Ly represents a simple bond or a divalent linking group, one of A ₁₁ and B ₁₁ is a monovalent heterocyclic group, and the other is a divalent heterocyclic group.
General formula (2);

In the general formula (2), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are each independently —SO—Z ₂ , —SO ₂ —Z ₂ , —SO ₂ NR ₂₁ R ₂₂ , sulfo group, —CONR ₂₁ R ₂₂ or —COOR ₂₁ is represented. Z ₂ each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or Represents a substituted or unsubstituted heterocyclic group. R ₂₁ and R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ each independently represent a monovalent substituent.
_{a 21 ~a 24, b 21 ~b} 24 each represent the number of substituents of X ₂₁ to X ₂₄ and Y ₂₁ to Y _24. a _{21 to} a ₂₄ each independently represents a number of 0 to 4, but they are not all 0 at the same time. b ₂₁ ~b ₂₄ represents the number of independently 0-4. Incidentally, when a ₂₁ ~a ₂₄ and b ₂₁ ~b ₂₄ represents the number of 2 or more, plural X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ may be the same as or different from each other to each other.
M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.
General formula (3);

In general formula (3), A represents a 5-membered heterocyclic ring.
B ₃₁ and B ₃₂ are each, = CR ₃₁ -, - or represents CR ₃₂ =, or either one nitrogen atom and the other = CR ₃₁ - or represents a -CR ₃₂ =.
R ₃₅ and R ₃₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group Each group may further have a substituent.
G, R ₃₁ and R ₃₂ are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, complex Ring oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino group) A heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or Aryl It represents a thio group, an alkyl or arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl or arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group, and each group may be further substituted.
R ₃₁ and R ₃₅ , or R ₃₅ and R ₃₆ may combine to form a 5- or 6-membered ring.
General formula (4);
A ^41- (N = N- (B ⁴¹ ) m) n-N = N-C ⁴¹
In the general formula (4), A ₄₁ , B ₄₁ and C ₄₁ each independently represents an optionally substituted aromatic group or heterocyclic group. m is 1 or 2, and n is an integer of 0 or more.