JP2005112877A - Ink for inkjet recording, ink set and inkjet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink for inkjet which hardly causes image bleeding even under high humidity conditions and hardly causes bleeding even when it gets wet with water after printed on a plain paper. <P>SOLUTION: The ink for inkjet comprises a water-soluble dye bearing at least a dissociable anionic group, water and/or a water-miscible organic solvent, and further contains at least one water-soluble organic compound bearing a cationic group capable of forming an ion pair with the dissociable anionic group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ink jet ink, an ink set, and an ink jet recording method that are excellent in image durability under high humidity conditions or wet conditions.

  In recent years, with the spread of computers, ink jet printers are widely used for printing on paper, film, cloth and the like not only in offices but also at home.

  Ink jet recording methods include a method of ejecting droplets by applying pressure with a piezo element, a method of ejecting droplets by generating bubbles in ink by heat, a method of using ultrasonic waves, or a droplet by electrostatic force. There is a method of sucking and discharging. As these inks for inkjet recording, water-based inks, oil-based inks, or solid (melting type) inks are used. Among these inks, water-based inks are mainly used from the viewpoints of production, handleability, odor, safety, and the like.

  The colorant used in these inks for ink jet recording has high solubility in solvents, high density recording, good hue, light, heat, air, water and chemicals. Excellent fastness, good fixability to image-receiving materials, low bleeding, excellent storage stability as ink, no toxicity, high purity, and availability at low cost It is requested. 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 the 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 such a dye has a problem that the formed image tends to bleed under high humidity conditions.

  It has also been found that there is a problem that when such ink is printed on plain paper and wetted with water after image formation, the dye spreads and spreads greatly.

  Accordingly, the problem to be solved by the present invention is to provide an ink jet ink, an ink ink set, and an ink jet recording method which are less likely to cause image blur even under high humidity conditions, and which do not easily blur even when wet on water after printing on plain paper. It is to be.

The above object of the present invention is achieved by an ink jet recording ink, an ink set, and an ink jet recording method having the following configurations.
1) An inkjet ink comprising at least a water-soluble dye having an anion-dissociating group, water and / or a water-miscible organic solvent, comprising a water-soluble organic compound having a cationic group capable of forming an ion pair with the anion-dissociating group Ink-jet ink comprising at least one kind.
2) The inkjet ink according to item 1, wherein the number of anion dissociation groups in one molecule of the dye is 3 or more.
3) The inkjet ink according to item 1 or 2, wherein at least one of the anion dissociation groups is a sulfo group.
4) The ink-jet ink according to any one of Items 1 to 3, wherein the water-soluble organic compound having a cationic group is a betaine compound.
5) The inkjet according to any one of Items 1 to 3, wherein the water-soluble organic compound having a cationic group is a water-soluble polymer obtained by polymerizing at least a monomer unit containing an aminic nitrogen atom. For ink.
6) An inkjet ink set comprising at least one ink according to any one of items 1 to 5.
7) An ink jet recording method, wherein image recording is performed on plain paper by an ink jet printer using at least one of the inks or ink sets described in the items 1 to 6.

  According to the present invention, it is possible to obtain an ink jet ink, an ink ink set, and an ink jet recording method which hardly cause bleeding of an image even under a high humidity condition, and which does not easily blur even when wet on water after printing on plain paper. In the present invention, the water-soluble organic compound having a cationic group significantly reduces ionicity, and the resistance to water is greatly improved.

Hereinafter, the present invention will be described in detail.
The ink-jet ink of the present invention uses a water-soluble dye having an anion dissociation group as a coloring material, and a water-soluble organic compound having a cation capable of forming an ion pair with the dye (water-soluble organic compound having a cationic group) ) At the same time.

Examples of water-soluble organic compounds having a cationic group include compounds containing protonated amine nitrogen atoms, compounds containing protonated sites such as guanidine and amidine, pyridine, pyrazine, quinoline, isoquinoline, pyrimidine, and pyridazine. And compounds having protonated compounds of hetero 6-membered aromatic compounds such as ammonium salts, amidinium salts, guanidinium salts, phosphonium salts, oxonium salts, thiuonium salts and the like.
Among them, a compound containing a protonated aminic nitrogen atom, a cation derived from a nitrogen atom, such as a protonated compound of guanidine, amidine, ammonium salt, amidinium salt, guanidinium salt, hetero 6-membered aromatic compound, etc. A compound is preferred.

Among these, as the water-soluble organic compound having a cationic group, a betaine compound is preferable. A betaine compound is a compound in which a cation and an anion coexist in the molecule.
The cation is preferably a cationic functional group such as the protonated nitrogen atom or nitrogen atom of the heteroaromatic ring, and the anion is an anion that can be dissociated in an aqueous solvent. Is preferred. As such an anion, any anionic dissociation group having a pKa of 13 or less in an aqueous solvent can be used. Examples of such a group include a carboxyl group, a sulfo group, a phosphoryl group, a phosphonic acid group, a sulfonamide group, an imide group, and a sulfoimide group. The group is preferably a group having a pKa of 10 or less, particularly preferably a group having a pKa of 7 or less, and the functional group is particularly preferably a carboxyl group or a sulfo group.

  The water-soluble organic compound having a cationic group used in the present invention, particularly the betaine compound, may be a low molecular compound, an oligomer or a polymer. In the case of a polymer, it may be a polymer having a betaine structure in a monomer unit, or may be a copolymer of a cationic monomer and an anionic monomer. In the case of selecting an oligomer or a polymer, either one that dissolves uniformly in an aqueous solvent or one that is used in a dispersed state can be selected, but a compound that dissolves uniformly is more preferable.

  When a low molecular weight compound is used, one containing an oil-soluble group in the molecule is more preferable. The oil-soluble group is a compound containing an alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group or the like having 4 or more, preferably 8 or more carbon atoms. Among these, as the betaine compound, a compound having surface activity can be more preferably used.

  Among them, compounds that can be particularly preferably used in the present invention are compounds represented by the following general formulas (A) to (C).

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.), heterocyclic group (which may be substituted, preferably a group having 2 to 20 carbon atoms, such as pyridyl group, quinolyl group, etc.). Each may be connected to each other to form a ring structure. 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. R ₁ , R ₂ , R ₃ and L may be connected to each other to form a ring. Examples of the ring include a piperidine ring, a morpholine ring, and an imidazole ring. A plurality of betaine structures may be contained via R _{1 to} R ₃ or L.

In the compound of the present invention, at least one of R _{1 to} R ₃ or L contains a group having 8 or more carbon atoms. Among these, those containing a long chain alkyl group in R _{1 to} R ₃ are particularly preferable.
General formula (C)

_{^{(R k) p -N- [L}} m - (COOM) 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.

The alkyl group represented by R is preferably a substituted alkyl, particularly preferably an amino group [two carboxyalkyl groups (for example, carboxymethyl group) -substituted amino groups] or an alkyl group substituted with an alkoxycarbonyl group.
When p is 2 or more, R may be the same or different, and L, R, and R may be connected 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. Of these, alkali metal ions or hydrogen atoms are particularly preferred.

q represents an integer of 1 or more (preferably 5 or less, more preferably 2 or less), and r represents an integer of 1 or more and 4 or less (preferably 1 or 2). k represents an integer of 0 or more and 4 or less (preferably 1), and m represents an integer of 1 or more (preferably 4 or less, more preferably 1). p represents an integer of 0 or more and 4 or less (preferably 1 or 2), and p + r is 3. 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.

  q and r each represents an integer of 1 or more. k and m represent an integer of 0 or more, and n represents an integer of 1 or more. p represents an integer of 0 or more, and p + r is 3.

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

Formula (D)
RN- (Q-COOM) ₂

  R and L are the same as described above. R is particularly preferably an alkyl group, and L is preferably an alkylene group.

  Preferred examples of the compound of the present invention will be enumerated below including polymer compounds, but the present invention is of course not limited thereto.

  The water-soluble organic compound having a cationic group of the present invention is contained in the ink in an amount of 0.01 to 20 mass percent, preferably 0.1 to 10 mass percent, and more preferably 0.5 to 5 mass percent.

  In the present invention, an anion dissociable water-soluble dye is used. Especially, it is preferable that it is a dye in which 3 or more dissociation groups are contained in 1 molecule. Particularly preferred is a dye containing 4 or more dissociating groups in one molecule.

  The dissociating group referred to here is a group that is synonymous in definition with the anionic group in the detailed description of the betaine compound. That is, it is an anion that can be dissociated in an aqueous solvent. As such an anion, any anionic dissociation group having a pKa of 13 or less in an aqueous solvent can be used. Examples of such a group include a carboxyl group, a sulfo group, a phosphoryl group, a phosphonic acid group, a sulfonamide group, an imide group, and a sulfoimide group. The group is preferably a group having a pKa of 10 or less, particularly preferably a group having a pKa of 7 or less, and the functional group is preferably a carboxyl group or a sulfo group. In particular, in the case of the dye used in the present invention, the dye has a sulfo group. Is preferred.

Various pigment skeletons can be used in the present invention.
The dye is preferably a dye whose oxidation potential is nobler than 1.0 V (vs SCE).
Examples of the dye include a-6 to a-9, a-11 to a-15, a-21 to a-23, a26 to a-29, and b-5 described in JP-A No. 2002-371214. , B-8, c-2 to c-5, d-1, e-4, e-5. f-1 to f-5 zeta dyes, phthalocyanine dyes described in JP 2002-309118 A, phthalocyanine dyes 1 to 39, 47 to 55, 57 to 59 described in JP 2003-12952 A, and the same Although it is preferable to use the dyes described in 1-6, 13-41 phthalocyanine dyes, etc. described in JP-A-2003-12956, preferable cyan dyes, magenta dyes, yellow dyes and black dyes are described in detail below. .

As the cyan dye, the following phthalocyanine dyes are preferably used.
The dye contained in the inkjet recording ink of the present invention is a phthalocyanine dye, preferably a water-soluble dye having an oxidation potential nobler than 1.0, and has good fastness to ozone gas. More preferably, it is a phthalocyanine dye represented by the formula (CI).
General formula (CI)

In the above general formula (CI);
X ₁ , X ₂ , X ₃ and X ₄ each independently represent —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , a sulfo group, —CONR ₁ R ₂ , or —CO ₂ R 1.
Z is 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 a substituted or unsubstituted group Represents a heterocyclic group. R1 and R2 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 An aryl group, or a substituted or unsubstituted heterocyclic group. When a plurality of Z are present, they may be the same or different.
Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a monovalent substituent.
Note that when one of X ₁ to X ₄ and Y1~Y4 there are a plurality, they may be the same or different.
a1 to a4 and b1~b4 each represent a number of substituents X ₁ to X ₄ and Y ₁ to Y _4, a1 to a4 are each independently an integer of 0 to 4, all 0 at the same time There is nothing and b1-b4 is an integer of 0-4 each independently. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.
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, 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) in order to lower the reactivity with ozone, which is an electrophile. The oxidation potential is preferably as noble, more preferably noble than the oxidation potential of 1.1 V (vs SCE), and most preferably nob of 1.2 V (vs SCE).

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.
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.

The value of Eox (oxidation potential) represents the ease of transfer of electrons from the sample to the electrode, and the greater the value (the higher the oxidation potential), the less transfer of electrons 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. In the present invention, in order to lower the reactivity with ozone, which is an electrophile, it is desirable to introduce an electron withdrawing group into the phthalocyanine skeleton to make the oxidation potential more noble. Therefore, by using Hammett's substituent constant σp value, which is a measure of the electron withdrawing property and electron donating property of a substituent, by introducing a substituent having a large σp value such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group. It can be said that the oxidation potential can be made more noble.
Also for the reason of such potential adjustment, it is preferable to use a phthalocyanine dye represented by the above general formula (CI).

  It is clear that the phthalocyanine dye having the oxidation potential is a cyan dye excellent in both light resistance and ozone resistance because the light resistance and ozone resistance conditions are satisfied.

Hereinafter, the phthalocyanine dye (preferably a phthalocyanine dye represented by formula (CI)) used in the present invention will be described in detail.
In the general formula (CI), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁ R ₂ , a sulfo group, —CONR 1 R ₂ , or —CO _2. R1 is represented. Among these substituents, —SO—Z, —SO ₂ —Z, —SO ₂ NR1R2 and —CONR1R2 are preferred, —SO ₂ —Z and —SO ₂ NR1R2 are particularly preferred, and —SO ₂ —Z is most preferred. . Here, when any one of a1 to a4 representing the number of substituents represents a number of 2 or more, a plurality of X _{1 to} X ₄ may be the same or different, and each of the above is independently Represents the group. X ₁ , X ₂ , X ₃ and X ₄ may each be the same substituent, or for example, X ₁ , X ₂ , X ₃ and X ₄ are all —SO ₂ —Z, and As in the case where each Z includes different ones, they 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 and —SO _2. NR1R2 may be included.

Z is independently substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted Alternatively, it represents an 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.
R1 and R2 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 An 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 R1 and R2 are hydrogen atoms.

The substituted or unsubstituted alkyl group represented by R1, R2 and Z 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 those similar to the substituents when Z _{below, R1, R2, Y 1,} Y 2, Y 3 and Y ₄ are capable of having 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 R1, R2 and Z 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 those similar to the substituents when Z _{below, R1, R2, Y 1,} Y 2, Y 3 and Y ₄ are capable of having 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 R1, R2 and Z 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 those similar to the substituents when Z _{below, R1, R2, Y 1,} Y 2, Y 3 and Y ₄ are capable of having 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 R1, R2 and Z 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 those similar to the substituents when Z _{below, R1, R2, Y 1,} Y 2, Y 3 and Y ₄ are capable of having 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 R1, R2 and Z is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent include those similar to the substituents when Z _{below, R1, R2, Y 1,} Y 2, Y 3 and Y ₄ are capable of having 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 R1, R2 and Z is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic groups represented by R1, R2 and Z are exemplified below in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. For example, in the case of pyridine, the 2-position is Substitution at the 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, examples of the substituent, if possible to have a later-described _{Z, R1, R2, Y 1} , Y 2, Y 3 and Y ₄ is a substituent The same thing as a substituent is mentioned. 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 ₁ , Y ₂ , Y ₃ and Y ₄ 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, carboxyl A 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, R ₁ , R 2, Y ₁ , Y ₂ , Y _3, and Y ₄ 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, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2- Methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (for example, acetamide, benzamide, 4- (3-t-butyl-4-) Hydroxyphenoxy) butanamide), alkyl Amino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), anilino groups (eg, phenylamino, 2-chloroanilino, ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfur Famoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octyl) Phenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carba Yl 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-tetrahydropyrani) Ruoxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group ( For example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide) N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropyl) Alkanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  When the phthalocyanine dye represented by the general formula (CI) 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.
a1~a4 and b1~b4 each represent the number of substituents of X ₁ to X ₄ and Y ₁ to Y _4. a1 to a4 each independently represents an integer of 0 to 4, but they are not all 0 at the same time. b1 to b4 each independently represents an integer of 0 to 4. Incidentally, when either a1~a4 and b1~b4 is an integer of 2 or more, any one of X ₁ to X ₄ and Y ₁ to Y ₄ will be present a plurality, they be the same or different It may be.
a1 and b1 satisfy the relationship of a1 + b1 = 4. Particularly preferred are combinations in which a1 represents 1 or 2 and b1 represents 3 or 2, and among them, the combination in which a1 represents 1 and b1 represents 3 is most preferred.
Each combination of a1 and b1, a1 and b1, and a1 and b1 has the same relationship as the combination of a1 and b1, and the 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.
In addition, Pc (phthalocyanine ring) may form a dimer (for example, Pc-MLM-Pc) or a trimer via L (a divalent linking group), and M at that time is Each may be the same or different.

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, And a group formed by combining them is preferred.
As for the preferred combination of substituents of the compound represented by the general formula (CI), 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.
Among the phthalocyanine dyes represented by the general formula (CI), a phthalocyanine dye having a structure represented by the general formula (CII) is more preferable.

The phthalocyanine dye represented by formula (CII) of the present invention is described in detail below.
In formula _{(CII), X 11 ~X 14} , Y 11 ~Y 18 is X ₁ to X in the general formula (CI) _4, and Y ₁ to Y ₄ are respectively the same, preferred examples are also the same is there. M ₁ has the same meaning as M in formula (CI), and preferred examples are also the same.
In general formula (CII), a11 to a14 are each independently an integer of 1 or 2, preferably satisfying 4 ≦ a11 + a12 + a13 + a14 ≦ 6, and particularly preferably when a11 = a12 = a13 = a14 = 1. .
X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may each be the same substituent, or for example, X ₁ , X ₂ , X ₃ and X ₄ are all —SO ₂ —Z, and each Z as in the case including the different and may be the same kind of is a substituent different partially from each other substituent or substituents different from each other, for example a -SO ₂ -Z and -SO ₂ NR1R2 May be included.

Among the phthalocyanine dyes represented by the general formula (CII), particularly preferred combinations of substituents are as follows.
X _{11 to} X ₁₄ are each independently preferably —SO—Z, —SO ₂ —Z, —SO ₂ NR 1 R ₂ or —CONR ₁ R ₂ , particularly preferably —SO ₂ —Z or —SO ₂ NR ₁ R ₂ , —SO ₂ -Z is most preferred.
Z is independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group Is most preferred. 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.

R1 and R2 are preferably each independently 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, a substituted alkyl group, A substituted aryl group and a substituted heterocyclic group are more preferable. However, it is not preferable that both R1 and R2 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 _{11 to} Y ₁₈ 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 group. Group 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.
a11 to a14 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.
In the present invention, the phthalocyanine dye represented by the general formula (CII) preferably has an anionic dissociation group (preferably 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 2 in one molecule of phthalocyanine dye, more preferably at least 2 sulfo groups and / or carboxyl groups, and 3 or more and 8 or less. Is particularly preferred.
As for the preferred combination of substituents of the compound represented by the general formula (CII), 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.
The chemical structure of the phthalocyanine dye of the present invention includes an electron-withdrawing group such as a sulfinyl group, a sulfonyl group, and a sulfamoyl group, at least one for each of the four benzene rings of phthalocyanine, and the σp value of the substituent of the entire phthalocyanine skeleton. It is preferable to introduce so that it may become 1.6 or more in total.

Regarding the Hammett's substituent constant σp value, reference can be made to the explanation of Z ^{1 in} the general formula (MIa) described later.
The phthalocyanine derivative represented by the general formula (CI) is inevitably different in the introduction position and number 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 (CI) and (CII) is defined by classifying into the following three types based on the substitution position. Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ , Y ₁₈ in the formula (CII) are defined as 1, 4, 5, 8, 9, ₁₂ , ₁₃ , and ₁₆ positions, 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 specific substituents 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: 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 The substitution type, α-position substitution type, and α, β-position mixed substitution type are used.
Examples of the phthalocyanine derivatives 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 compounds represented by the general formula (CI) of the present invention are 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, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution 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.
Examples of the phthalocyanine compound represented by the general formula (CII) of the present invention include a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula represented by the general formula (CIII). 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 (CIII): can do.

In the above formulas, Xp corresponds to X ₁₁ , X ₁₂ , X ₁₃ or X ₁₄ in the general formula (CII). Yq and Yq ′ correspond to Y ₁₁ , Y ₁₂ , Y ₁₃ , Y ₁₄ , Y ₁₅ , Y ₁₆ , Y ₁₇ or Y ₁₈ in the general formula (CII), 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.
Formula (CIII): M- (Y) d
In the general formula (CIII), M has the same meaning as M in the general formulas (CI) and (CII), and Y is a monovalent or divalent coordination such as a halogen atom, acetate anion, acetylacetonate, oxygen, etc. Child 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 (CI). It is extremely superior compared to
The phthalocyanine compound represented by the general formula (CII) 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 ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ 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 (CII), these dyes having mutually different electron-withdrawing substituents are particularly preferable because they can adjust the solubility of the dye, the association property, the stability with time of the ink, and the like.
In the present invention, it has been 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., compared to the α, β-position mixed substitution type. there were.
Specific examples of the phthalocyanine dyes represented by the general formulas (CI) and (CII) include those described in JP-A Nos. 2002-309118, 2003-12952, and 2003-12956, and international publications. Illustrative compounds I-1 to I-190 in the pamphlet of No. 03/066756 are listed, but the phthalocyanine dye used in the present invention is not limited to these examples.

The phthalocyanine dye represented by the general formula (CI) can be synthesized according to the aforementioned patent. Moreover, the phthalocyanine dye represented by the general formula (CII) is not limited to the synthesis method described above, 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, dye intermediate and synthetic route are not limited to these.
The ink for inkjet recording of the present invention preferably contains 0.2 to 20% by mass of the phthalocyanine dye, more preferably 0.5 to 15% by mass.
The ink for inkjet recording of the present invention can be produced by dissolving and / or dispersing a phthalocyanine dye in an aqueous medium. In the present invention, the “aqueous medium” refers to water or a mixture of water and a small amount of a water-miscible organic solvent, if necessary, a wetting agent (preferably a surfactant as a dissolution aid or a dispersion aid), stable. Means added with additives such as preservatives and preservatives.

The magenta ink used in the inkjet recording ink of the present invention has a magenta dye selected from azo dyes dissolved or dispersed in an aqueous medium, and has an absorption maximum in a spectral region of 500 to 580 nm in the aqueous medium. And a dye having an oxidation potential nobler than 1.0 V (vs SCE).
The first structural feature of the preferred dye of this azo dye is that it is a dye having a chromophore represented by the general formula (heterocycle A) -N = N- (heterocycle B). 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, the 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 chromophore has an aromatic ring amino group or heterocyclic amino group structure, specifically an anilino group or a heterylamino group.
A fourth preferred structural feature is having a steric structure. Specifically, it is described in Japanese Patent Application No. 2002-12015.
Among the preferable structural features of the azo dyes described above, the dyes represented by the following general formula (MI) are most preferable for achieving the object of the present invention.
General formula (MI)

In general formula (MI), A represents a 5-membered heterocyclic group.
B ¹ and B ² are each = CR ¹ -, - or represents a CR ² =, or either one nitrogen atom and the other = CR ¹ - or an -CR ² =. R ⁵ and R ⁶ 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, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted.
G, R ¹ and R ² each independently represents a hydrogen atom or a substituent, which includes a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a 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, aryloxy Carbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio Group, ally Represents a ruthio 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 substituted.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.

The dye of the general formula (MI) will be described in more detail.
In general formula (MI), A represents a 5-membered heterocyclic group. Examples of heteroatoms in the heterocycle 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. Preferable examples of the heterocyclic ring include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a 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 general formulas (a) to (f), R ⁷ to R ²⁰ represent the same substituents as G, R ¹ and R ² in the general formula (MI).
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 (MI), B ¹ and B ² each represent = CR ¹ -and -CR ² =, or either one represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =, It is more preferable that each represents = CR ^1- , -CR ² =.
R ⁵ and R ⁶ 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, alkylsulfonyl Represents a group, an arylsulfonyl group, or a sulfamoyl group, and the hydrogen atom of each substituent may be substituted.
R ⁵ and R ⁶ are preferably a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkylsulfonyl group or arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an 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, R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

G, R ¹ and R ² each independently represents a hydrogen atom or a substituent, which includes a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a 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, aryloxy Carbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group , Arylsulfonylamino group , Heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group, arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, Alternatively, it represents a sulfo group, and the hydrogen atom of each substituent may be substituted.
G is hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (alkylamino group, arylamino group, heterocyclic amino group) An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom, a halogen atom, an alkyl group. Group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, amino group or acylamino group, among which hydrogen atom, amino group (preferably anilino group) or acylamino group is most preferred. The hydrogen atom of each substituent may be substituted.

Preferable examples of R ¹ and R ² include a hydrogen atom, alkyl group, halogen atom, alkoxycarbonyl group, carboxyl group, carbamoyl group, hydroxy group, alkoxy group, and cyano group. The hydrogen atom of each substituent may be substituted.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.
When A has a substituent, or when the substituent of R ¹ , R ² , R ⁵ , R ⁶ or G further has a substituent, the substituents mentioned for G, R ¹ and R ² above You can give a group.
The dye of the general formula (MI) used in the present invention contains an anionic dissociating group, and an anionic dissociating group (as a substituent at any position on A, R ¹ , R ² , R ⁵ , R ⁶ , G) It preferably has an ionic hydrophilic 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).

The terms (substituents) used in this specification will be described. These terms are common even between different symbols in the general formula (MI) and the general formula (MIa) 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. In this specification, “substituted” used for “substituted alkyl group” and the like means that a hydrogen atom existing in “alkyl group” or the like is substituted with the substituents mentioned in G, R ¹ and R ² above. Indicates.
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 of the aromatic group is preferably 6-20, and more preferably 6-16.
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 of the substituted heterocyclic group 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, and an ionic hydrophilic group. 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. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group, and the alkyl group, the aryl group, and the 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, respectively. The alkylsulfonylamino group and arylsulfonylamino group are preferably an alkylsulfonylamino group having 1 to 20 carbon atoms and an arylsulfonylamino group having 7 to 20 carbon atoms. 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, respectively. 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, respectively. 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.

In the present invention, a particularly preferred structure is represented by the following general formula (MIa).
General formula (MIa)

In the formula, R ¹ , R ² , R ⁵ and R ⁶ have the same meanings as those in the general formula (MI).
R ³ and R ⁴ 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, alkylsulfonyl Represents a 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 ¹ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ¹ 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. Specific examples of the preferred substituent include an electron-withdrawing substituent described later. Among them, 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, an arylsulfonyl group having 6 to 20 carbon atoms, 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.
Z ² represents a hydrogen atom or a substituent, and the substituent represents an aliphatic group, an aromatic group, or a heterocyclic group. Z ² 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 (MIa) may be substituted. Examples of the substituent include the substituents described in the general formula (MI), groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups.
Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule was found in 1935 by L. L. 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 "Areas in Chemistry", Special Issue 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 includes substituents that would be included in the range when measured based on Hammett's rule. In addition, the general formula (1a) of the present invention includes those that are not benzene derivatives, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value is used in this sense.

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). .
Examples of the electron-withdrawing group having a Hammett σp value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chlorophenoxycarbonyl) in addition to the above. ), An alkylsulfinyl group (for example, n-propylsulfinyl), an arylsulfinyl group (for example, phenylsulfinyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), a halogenated 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 σp value of 0.20 or more include a halogen atom in addition to the above.

A particularly preferred combination of substituents as the azo dye represented by the general formula (MI) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ⁵ and R ⁶ . 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 ⁵ and R ⁶ 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 ¹ and B ² are ═CR ¹ — and —CR ² ═, respectively, and R ¹ and R ² are each preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxyl group, an alkoxy group. Group, an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group, or a carbamoyl group.

  The preferred combination of substituents of the compound represented by the general formula (MI) is preferably a compound in which at least one of various substituents is the above preferred group, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  Specific examples of the compound (azo dye) represented by the general formula (MI) include a-1 shown in Tables 1 to 13 in JP-A No. 2002-371214 and WO 03/066756. -A-46, b-1 to b-8, c-1 to c-5, d-1 to d-5, e-1 to e-5, f-1, and f-2. The azo dye used in the invention is not limited to these examples.

  The ink composition for ink jet recording of the present invention (also simply referred to as “ink” in the present invention) is obtained by dissolving and / or dispersing at least one of the azo dyes in an aqueous medium. It contains 0.2-20 mass%, More preferably, it contains 0.5-15 mass%.

The azo dye used in the present invention is substantially water-soluble. “Substantially water-soluble” means that 2% by mass or more dissolves in water at 20 ° C.
In addition, in the ink composition for inkjet according to the present invention, other magenta dyes can be used in combination with the azo dye (magenta dye).
Examples of magenta dyes that can be used in combination include aryl or heteryl azo dyes having phenols, naphthols, and anilines as coupling components (other than general formula (MI) of the present invention); for example, pyrazolones and pyrazolotriazoles as coupling components Azomethine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, such as naphthoquinone, anthraquinone, anthrapyridone, etc. Quinone dyes such as condensed polycyclic dyes such as dioxazine 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, or may be a polymer cation having these in a partial structure. In the ink composition containing the compound of the general formula (MI) of the present invention, other dyes are used in combination within the range satisfying the ink deposition test of the present invention.

Hereinafter, the yellow dye useful in the present invention will be described in detail.
The yellow dye used in the present invention is preferably a dye having an oxidation potential nobler than 1.0 V (vs SCE) and more nobler than 1.1 V (vs SCE) in terms of fastness and fastness to ozone gas. Certain dyes are more preferred, and dyes that are noble above 1.2 V (vs SCE) are particularly preferred. As the kind of dye, an azo dye satisfying the above physical property requirements is particularly preferable.
The oxidation potential value (Eox) can be measured in the same manner as in the phthalocyanine dye.

  The value of Eox represents the ease of electron transfer from the sample to the electrode, and the greater the value (the higher the oxidation potential), the less electron transfer from the sample to the electrode, in other words, the less easily oxidized. 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. In the present invention, in order to lower the reactivity with ozone, which is an electrophile, 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, λmax is from 390 nm to 470 nm, and the ratio I (λmax + 70 nm) / I (λmax) between the absorbance I (λmax) of λmax and the absorbance I (λmax + 70 nm) of λmax + 70 nm is 0.20 or less. The yellow dye is preferably 0.15 or less, more preferably 0.10 or less. In addition, the absorption wavelength and absorbance defined here show values in a solvent (water or ethyl acetate).

As the dye satisfying such oxidation potential and absorption characteristics, those represented by the following general formula (Y1) are preferable.
Formula (Y1) (A-N = NB) n-L
In the formula, A and B each independently represent 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 represents an integer selected from 1 or 2, and 2 is more preferable. L represents a hydrogen atom, a monovalent substituent, a simple bond or a divalent linking group. However, when n is 1, L represents a hydrogen atom or a monovalent substituent, and both A and B are monovalent heterocyclic groups. When n is 2, L represents a simple bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group.

  In the general formula (Y1), the heterocyclic ring represented by A includes 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.

  The heterocyclic ring represented by B includes pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzo Examples include imidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, or benzoisoxazole are preferable, quinoline, More preferred are thiophene, pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, or thiadiazole, pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, or 1,3, 4-thiadiazole is particularly preferred.

Substituents substituted for A and B are halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, alkoxy groups, aryls. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group Group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group or the following ionic hydrophilic groups Take an example.
Examples of the monovalent substituent represented by L include the substituents substituted on the above A and B or the following ionic hydrophilic groups. Examples of the divalent linking group represented by L 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 are the substituents mentioned in the substituents substituted for A and B, or the following ionic hydrophilic groups You may have.

  The dye of the general formula (Y1) has an anionic dissociation group in the molecule, and preferably has at least one ionic hydrophilic group in the anionic dissociation 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 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 (Y1), dyes in which A—N═NB corresponds to the general formulas (Y2), (Y3), and (Y4) are preferable.
General formula (Y2)

In general formula (Y2), 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, and R2 represents 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.
General formula (Y3)

In General Formula (Y3), 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, Za is —N =, -NH-, or -C (R11) =, Zb and Zc each independently represent -N = or -C (R11) =, R11 represents a hydrogen atom or a non-metallic substituent, R6 represents a heterocyclic group.
General formula (Y4)

  In the general formula (Y4), R7 and R9 are each independently a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, or an ion. 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 group, an arylthio group. Represents a group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl, an arylsulfonyl group, an acyl group, an amino group, a hydroxy group, or an ionic hydrophilic group, and R10 represents a heterocyclic group.

  In the general formulas (Y2), (Y3) and (Y4), the alkyl group represented by R1, R2, R3, R5, R7, R8 and R9 includes an alkyl group having a substituent and an unsubstituted alkyl group. It is. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Examples of the substituent include a hydroxyl 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 a cyclohexyl group.
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 an alkyl group, an alkoxy group, a halogen atom, an alkylamino 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 an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and p-tolylthio.

R2 and heterocyclic group represented by the below-mentioned R ²² are 5- or 6-membered heterocyclic ring is preferably they 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 those described later for the aryl group. Preferred heterocycles are 6-membered nitrogen-containing aromatic heterocycles, and triazine, pyrimidine and phthalazine can be mentioned 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 hydroxyl 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 an alkoxy group and an ionic hydrophilic group. 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 an ionic hydrophilic group. Examples of the acylamino group include acetamide, propionamide, benzamide and 3,5-disulfobenzamide.

The sulfonylamino group represented by R8 includes a sulfonylamino group having a substituent and an unsubstituted sulfonylamino group. 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.

Examples of the alkylsulfonyl and arylsulfonyl groups represented by R8 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 formula (Y1), 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 (Y3), Za represents -N =, -NH-, or -C (R11) =, 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 (Y3) are shown below.

  Examples of the substituent when each substituent described above may further have a substituent include the substituents that may be substituted on the heterocyclic rings A and B in the general formula (Y1) described above. I can do it.

  The dyes represented by the general formulas (Y2) to (Y4) preferably have at least one ionic hydrophilic group in the molecule. In addition to the dyes in which at least one of R1, R2, R3, R5, R7, R8 and R9 in the general formulas (YY2) to (Y4) is an ionic hydrophilic group, the general formulas (Y2) to (Y In Y4), dyes in which R1 to R11 further have an ionic hydrophilic group as a substituent are included.

Of the above general formulas (Y2), (Y3), and (Y4), preferred is the general formula (Y2), and among these, those represented by the following general formula (Y2-1) are particularly preferred.
General formula (Y2-1)

In formula (Y2-1), 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 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. Each substituent may be further substituted.
In the general formula (Y2-1), a dye having an ionic hydrophilic group is preferable.
As preferred dyes used in the present invention, Japanese priority application of Japanese Patent Application No. 2002-229222: Japanese Patent Application No. 2003-286844, Japanese Patent Application No. 2002-211683, Japanese Patent Application No. 2002-124832, Japanese Patent Application Laid-Open No. 2003-128953, Although what was described in Unexamined-Japanese-Patent No. 2003-41160 is mentioned, The compound illustrated below is especially preferable especially. In addition, the dye which can be used for this invention is not limited to these. These compounds are disclosed in Japanese Patent Application No. 2002-229222, Japanese Patent Application No. 2003-286844, Japanese Patent Application No. 2002-211683, Japanese Patent Application No. 2002-124832, Japanese Patent Application Laid-Open No. 2003-128953, Japanese Patent Application Laid-Open No. 2003-41160, Japanese Patent Application Laid-Open No. Hei 2- 24191 and JP-A No. 2001-279145 can be used as a reference.

  Specific examples of preferable dyes used in the present invention include YI-1 to YI-103 of Japanese Patent Application No. 2003-131581 and Illustrative Dyes 1 to 75 of Japanese Patent Application No. 2003-286844. The dye used in the invention is not limited to these specific examples.

  The ink for inkjet recording preferably contains 0.2 to 20% by mass of the yellow dye, and more preferably contains 0.5 to 15% by mass.

Hereinafter, the black dye of the present invention will be described in detail.
In the black ink for ink jet recording of the present invention, first, λmax is from 500 nm to 700 nm, and the half-value width (Wλ _{, 1/2} ) in the absorption spectrum of a diluted solution normalized to an absorbance of 1.0 is 100 nm or more (preferably 120 nm). The dye (L) which is 500 nm or less and more preferably 120 nm or more and 350 nm or less is used.

When 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 be emphasized. 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 preferable to use together with a dye (S) having main absorption 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 an aqueous medium, and the black ink for ink jet recording is preferable. That is, 1) excellent weather resistance, and / Or 2) In order to satisfy the fact that the black balance is not lost even after fading, an ink satisfying the following conditions is prepared.

First, the black square symbol of 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. From this time (t) until the reflection density (D _vis ) reaches 80% of the initial reflection density value, the printed matter is forcibly faded using an ozone fading tester capable of always generating 5 ppm of ozone. The forced fading rate constant (k _vis ) is obtained from the relational expression “0.8 = exp (−k _vis · t)”.
In the present invention, the rate constant (k _vis ) is 5.0 × 10 ⁻² [hour ⁻¹ ] or less, preferably 3.0 × 10 ⁻² [hour ⁻¹ ] or less, more preferably 1.0 × 10 ^{−. 2} [hour ^-1 ] An ink having the following ^value is prepared. (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 but 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 print is forcibly faded using an ozone fading tester capable of always generating 5 ppm of ozone in accordance with the above method, and each reflection density (D _R , D _G , D _B ) is 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 ink is prepared so that the ratio (R) is 1.2 or less, preferably 1.1 or less, and more 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.

  In addition, the oxidation potential of at least one dye used for the black ink is nobler than 1.0 V (vs SCE), preferably nobler than 1.1 V (vs SCE), more preferably 1.2 V (vs SCE). Noble, 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)

The oxidation potential is in N, N-dimethylformamide containing 0.1 mol · dm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the compound is 1 × 10 ⁻³ mol · dm ⁻³ ). SCE (saturated calomel electrode) is used as a reference electrode, a graphite electrode is used as a working electrode, and a platinum electrode is used as a counter electrode, and values measured by direct current polarography are used. 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 may be deviated by several tens of mil volts due to the influence of the inter-liquid potential difference or the liquid resistance of the sample solution, but the potential measured by calibrating with a standard sample (for example, hydroquinone). The reproducibility of the value of can be guaranteed.

Furthermore, as the black ink, it is preferable to use an azo dye described in the following general formula (BK1).
General formula (BK1)

  In the general formula (BK1), A, B and C each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A and C are monovalent groups) , B is a divalent group). m is 1 or 2, and n is an integer of 0 or more.

  The azo dye described in the general formula (BK1) 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, a dye (S) having a λmax of 350 nm to 500 nm can also be cited as corresponding to the dye of the general formula (BK1). Preferably, at least one of the dyes (L) is a dye of the general formula (BK1), but particularly preferably at least one of the dyes (L) and (S) is a dye of the general formula (BK1). It is preferable that 90% by mass of the total dye in the ink is the dye of the general formula (BK1). (Condition 4)

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

  Next, among the dyes represented by the general formula (BK1), those corresponding to the dye (L) will be described in detail.

In the general formula (BK1), A, B and C each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A and C are monovalent groups) , B is a divalent group). m is 1 or 2, and n is an integer of 0 or more.
Among them, a compound in which m and n are each 1 or 2 is preferable, and at that time, at least two of A, B and C are preferably an unsaturated heterocyclic group which may be substituted. Among these, m and n = 1 are particularly preferable, and at least B and C are unsaturated heterocyclic groups.
The azo dye represented by the general formula (BK1) is particularly preferably a dye represented by the following general formula (BK2).
General formula (BK2)

In the general formula (BK2), A and B have the same meanings as in the general formula (BK1). B ₁ and B ₂ each represent = CR ₁ -and -CR ₂ =, or either one represents a nitrogen atom and the other represents = CR ₁ -or -CR ₂ =.
G, R ₁ and R ₂ 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 (alkylamino) 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 Represents 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 Also good.
R ₅ and R ₆ 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 ₅ and R ₆ are not simultaneously hydrogen atoms.
R ₁ and R ₅ , or R ₅ and R ₆ may be bonded to form a 5- to 6-membered ring.
The azo dye represented by the general formula (BK2) is preferably a dye represented by the following general formula (BK3).
General formula (BK3)

In the general formula (BK3), R ₇ and R ₈ have the same meaning as R _{1 in the} general formula (BK2).

  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. 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 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 an 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 (BK1), (BK2), and (BK3) will be described.
In the following description, what has already been described applies to the group and the substituent.
In the general formula (BK1), A, B and C are each independently an optionally substituted aromatic group (A and C are monovalent aromatic groups such as aryl groups; B is a divalent aromatic group; A group such as an arylene group) or an optionally substituted heterocyclic group (A and C are monovalent heterocyclic groups; B 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.
Moreover, at least two of A, B, and C are preferably heterocyclic groups.

A preferred heterocyclic group for C includes an aromatic nitrogen-containing 6-membered heterocyclic group represented by the following general formula (BK4). When C is an aromatic nitrogen-containing 6-membered heterocyclic group represented by the following general formula (BK4), the general formula (BK1) corresponds to the general formula (BK2).
General formula (BK4)

In the general formula (BK4), B ₁ and B ₂ each represent = CR ₁ -and -CR ₂ =, or either one represents a nitrogen atom and the other represents = CR ₁ -or -CR ₂ =. More preferably, each represents = CR _1- , -CR ₂ =.
R ₅ and R ₆ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, sulfamoyl group. Each group may further have a substituent. Preferable substituents represented by R ₅ and R ₆ 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 ₅ and R ₆ are not simultaneously hydrogen atoms.

G, R ₁ and R ₂ 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 (alkylamino) 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 Each represents a alkyl group and an arylthio group, a heterocyclic thio group, an alkyl and arylsulfonyl group, a heterocyclic sulfonyl group, an alkyl and 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 include a hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (alkylamino group, aryl group) An amino group, a heterocyclic amino group), an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, more preferably A hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group (including an alkylamino group, an arylamino group, a heterocyclic amino group) or an acylamino group, among which a hydrogen atom, An anilino group and an acylamino group are most preferred. Each group may further have a substituent.

Preferable substituents represented by R ₁ and R ₂ 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 ₁ and R ₅ , or R ₅ and R ₆ may combine to form a 5- to 6-membered ring. Examples of the substituent in the case where each substituent represented by A, R ₁ , R ₂ , R ₅ , R ₆ , and G further has a substituent include the substituents exemplified for G, R ₁ , and R ₂ above. be able to. Further, it has an anionic dissociation group (preferably an ionic hydrophilic group) as a substituent at any position on A, R ₁ , R ₂ , R ₅ , R ₆ and G.
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).

  Preferred heterocycles when B is a ring structure include thiophene rings, thiazole rings, imidazole rings, benzothiazole rings, and thienothiazole rings. Each heterocyclic group may further have a substituent. Of these, thiophene rings, thiazole rings, imidazole rings, benzothiazole rings, and thienothiazole rings represented by the following general formulas (a) to (e) are preferable. When m = n = 1, B is a thiophene ring represented by (a), and C is a structure represented by the general formula (BK4), the general formula (BK1) is represented by the general formula This corresponds to (BK3).

In the general formulas (a) to (e), R ₉ to R ₁₇ represent a substituent having the same meaning as G, R ₁ and R ₂ in the general formula (BK2).

In the present invention, a particularly preferred structure is represented by the following general formula (BK5).
General formula (BK5)

In the formula, Z ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁ 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 0.0. Specific examples of the preferred substituent include an electron-withdrawing substituent described later. Among them, 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, an arylsulfonyl group having 6 to 20 carbon atoms, 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 ₁ , R ₂ , R ₅ and R ₆ have the same meaning as in the general formula (BK2). R ₃ and R ₄ 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 (BK5) 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 (BK2), the groups exemplified for G, R ₁ and R ₂ , and ionic hydrophilic groups.
Here, Hammett's substituent constant σ _p value used in this specification will be described. Hammett's rule was found in 1935 by L. L. 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 (McGraw-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 σ _p, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. The general formula (1) or (2) of the present invention includes those that are not benzene derivatives, but the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. . In the present invention, the σ _p value is used in this sense.

Examples of the electron-withdrawing group having a Hammett substituent constant σ _p 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)). it can.
In addition to the above, an electron-withdrawing group having a Hammett σ _p 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-chlorophenoxy). Carbonyl), alkylsulfinyl group (for example, n-propylsulfinyl), arylsulfinyl group (for example, phenylsulfinyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated alkyl group (For example, trifluoromethyl).
As an electron-withdrawing group having a Hammett substituent constant σ _p 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), Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy group), halogenated alkylthio groups (for example, difluoromethylthio), An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with an electron-withdrawing group having two or more σ _p values of 0.15 or more, and a heterocycle (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) Door can be.
Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more include a halogen atom in addition to the above.

A particularly preferred combination of substituents as the azo dye represented by the general formula (BK3) is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group as R ₅ and R ₆ . 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 ₅ and R ₆ 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, an amino group. Group, an acylamino group.
A is preferably an aromatic group, a pyridine ring, a pyrazole ring, an imidazole ring, an isothiazole ring, a benzoisothiazole ring, a thiadiazole ring, a thiazole ring, a benzothiazole ring, a triazole ring, and further an aromatic group, pyridine A ring, an isothiazole ring, a benzoisothiazole ring, a thiadiazole ring and a benzothiazole ring, and most preferably an aromatic group, a pyridine ring and a benzothiazole ring.
B ₁ and B ₂ are ═CR ₁ — and —CR ₂ ═, respectively, and R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a 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.

  In addition, about the preferable combination of a substituent of the compound represented by the said general formula (BK1), 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 (BK1) include Bk-1 to Bk-75 of Japanese Patent Application No. 2003-131581, but the azo dye used in the present invention is limited to these examples. In addition, the carboxyl group, the phosphono group, and the sulfo 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 ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidinium ions, tetramethylphosphonium).

  The dyes represented by the general formulas (BK1), (BK2), (BK3), and (BK5) can be synthesized by a coupling reaction between a diazo component and a coupler. As the main synthesis method, it can be synthesized by the method described in Japanese Patent Application No. 2002-113460.

  When 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 be emphasized. 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, a preferable black is realized in combination with a dye or pigment having a main absorption in the yellow region. As a yellow dye, a direct dye or an acid dye represented by a commonly used azo dye or azomethine dye can be used. As the pigment, an aqueous dispersion of a general pigment having a pigment number can be used in combination. Among these, it is particularly preferable to use a dye represented by the general formula (BK1) as the above-described short wave side dye (S).

  Among the dyes represented by the general formula (BK1), azo dyes where m = n = 0 can be mentioned as preferred as the short wave side dye (S). At this time, A and C are preferably heteroaromatic rings. Next preferred are azo dyes where m = n = 1.

In any case, a dye having an oxidation potential (Eox) of 1.0 V (vsSCE) is preferable, and a dye having an Eox of 1.2 V (vsSCE) is particularly preferable.
In the black ink, at least two kinds of long-wave side dyes can be used in combination.

It is also possible to produce a black ink by using another dye in combination.
As a black ink for inkjet recording, the dye of the general formula (BK1) is contained in an amount of 0.2 to 25% by mass, preferably 0.5 to 15% by mass.

  As dyes having λmax of 350 nm to 500 nm, yellow dyes and yellow pigments described later are also used.

  The black dye is substantially water-soluble or water-dispersible. In particular, the ink composition containing the black dye of the present invention is preferably a solution type ink composition in which the dye is water-soluble. Specifically, the solubility of the dye in water at 20 ° C. is preferably 2% by mass, more preferably 5% by mass or more.

  The dye other than the black dye in the present invention is preferably substantially water-soluble or water-dispersible. Specifically, the solubility of the dye in water at 20 ° C. is preferably 2% by mass or more, and more preferably 5% by mass or more.

  Further, when two or more types of ink are prepared, one can be a light light ink and the other can be a dark ink. In the present invention, it is also possible to make such an ink separately. In addition, it is possible to prepare ink compositions having almost the same concentration.

  Examples of usable dyes other than the black dye include triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, azomethine dyes, azo dyes, cyanine dyes, merocyanine dyes, oxonol dyes, and other dyes known in the art. It is possible to use it in combination so that it is preferably a black dye. Of these, azo dyes are particularly preferred.

  More specifically, yellow dyes include, for example, aryls or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, open-chain active methylene compounds as coupling components; Azomethine dyes having a type active methylene compound; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, etc. Examples thereof include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes. 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. Examples thereof include 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.

Examples of water-soluble dyes include direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes. As a preferable thing,
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.

  In the ink of the present invention, other dyes can be used in combination with the dye in order to adjust the color tone for obtaining a full-color image. Examples of other pigments that can be used in combination include the above-mentioned dyes and the following pigments.

  As the pigment used in the present invention, in addition to commercially available pigments, 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 Japan Pigment Technology Association (1989), "Latest Pigment Applied Technology" CMC Publishing (1986), "Printing Ink Technology" CMC Publication (1984), Industrial Organic Pigments (VCH Verlagsgesellschaft, 1993) by W. Herbst and K. Hunger. Specifically, for 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, white pigment CI Pigment White 4,6,18,21 and the like.

  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-based CI Pigment Yellow 120, 151, 154, 156, 180, etc., among which preferable ones do not use benzidine-based compounds), iso Indoline / 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) Is 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 present invention may be the above-mentioned 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.
(1) Properties and applications of metal soap (Sachishobo)
(2) Printing ink printing (CMC Publishing 1984)
(3) Latest pigment application technology (CMC Publishing 1986)
(4) U.S. Patent Nos. 5,554,739 and 5,571,311
(5) 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 US patent of (4) above Self-dispersing pigments and encapsulated pigments prepared by the method described in the Japanese patent (5) above are particularly effective because dispersion stability can be obtained without using an extra dispersant in the ink. It is.

In 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 present invention is preferably in the range of 0.01 to 10 μm, more preferably 0.05 to 1 μm after dispersion.
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).

  Examples of water-miscible organic solvents (including water-soluble organic solvents) used in the present invention include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, Hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane Triols, thiodiglycols), glycol derivatives (eg ethylene glycol monomethyl ether, ethylene glycol monoethyl) Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether Acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine) , Ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone) N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together. In the present invention, among these, a water-miscible organic solvent (preferably a water-soluble organic solvent) having a boiling point of 150 ° C. or higher (preferably 200 ° C. or higher) is preferably used.

Next, other components that can be contained in the ink composition for inkjet recording of the present invention will be described.
The ink for ink jet recording (composition) can contain a surfactant, thereby adjusting the liquid physical properties of the ink composition, thereby improving the ejection stability of the ink composition and improving the water resistance of the image. It is possible to provide an excellent effect in improving the ink resistance and preventing bleeding of the printed ink composition.
Examples of the surfactant include anionic surfactants such as sodium dodecyl sulfate, sodium dodecyloxysulfonate, sodium alkylbenzene sulfonate, and cationic surfactants such as cetylpyridinium chloride, trimethylcetylammonium chloride, and terabutylammonium chloride. And nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, and polyoxyethylene octylphenyl ether. Among these, nonionic surfactants are particularly preferably used.

  The content of the surfactant is 0.001 to 15% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass with respect to the ink composition.

  The ink composition for ink jet recording obtained in the present invention includes a drying inhibitor for preventing clogging due to dry operation at an ink jetting port, a penetration accelerator for allowing the ink to permeate the paper better, and UV absorption. Use appropriate amounts of additives such as additives, antioxidants, antifoaming agents, viscosity modifiers, surface tension modifiers, dispersants, dispersion stabilizers, antifungal agents, rust inhibitors, pH adjusters, etc. Can do.

  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 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as 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, the effect is sufficient, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding 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. Cinnamic acid compounds described in JP-A-48-30492, JP-A-56-21141, JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368. And triazine compounds described in JP-A-10-182621, JP-A-8-501291, etc. Jar No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  In the present invention, various kinds of 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, Nos. VII to I, J; 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.

  The antifoaming agent used in the present invention is a copolymer of dimethylpolysiloxane and polyalkylene oxide, and includes a pendant type, a terminal-modified type, an ABN type, and the like, but a pendant type is preferable. Examples of these copolymers include FZ-2203, -2207, -2222, and -2166 (trade name, manufactured by Nihon Unicar).

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 salts thereof. 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. As a pH adjuster, an organic base, an inorganic alkali, etc. are mentioned as a basic thing, An organic acid, an inorganic acid, etc. are mentioned as an acidic thing.
Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, and dimethylethanolamine. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc.), carbonates (for example, sodium carbonate, sodium hydrogen carbonate, etc.), ammonium and the like. Examples of the organic acid include acetic acid, propionic acid, trifluoroacetic acid, and alkylsulfonic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like.

In the present invention, nonionic, cationic or anionic surfactants may be mentioned as surface tension adjusting agents in addition to the betaine compounds containing the surfactants. 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.
The surface tension of the ink used in the present invention is preferably 20 to 50 mN / m or less, more preferably 20 to 40 mN / m or less at 25 ° C. for both dynamic and static surface tension. If the surface tension exceeds 50 mN / m, the ejection quality, bleeding at the time of color mixing, print quality such as whiskers, etc. will be significantly reduced. If the surface tension of the ink is 20 mN / m or less, there may be a printing failure due to ink adhesion to the hard surface during ejection.

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), Chapter 9 and “Chemicals for Inkjet Printers (98 Supplement)-Material Development Trends and Perspective Survey” (CMC, 1997) 162- It is described on page 174.

When preparing the ink of the present invention, in the case of a water-soluble ink, it is preferably first dissolved in water. Thereafter, various solvents and additives are added, dissolved and mixed to obtain a uniform ink.
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.

The image receiving material for receiving the ink droplet of the present invention will be described below.
The image receiving material refers to a material comprising at least a support having a function of receiving ink on its surface and forming an image.
The image receiving material may be composed of only the support, or an image receiving layer on the surface of the support or a back layer on the opposite side of the image receiving layer. In the present invention, the effect of the invention becomes clearer with plain paper, which is an image receiving material substantially composed of only a support.

 Examples of the support include recording paper and recording film. The support in the recording paper and the recording film is made of a fiber material. Examples of the fiber material include chemical pulps such as LBKP and NBKP, mechanical pulps such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and DIP. Examples thereof include single or a mixture of natural plant fibers other than wood, synthetic fibers, inorganic fibers, etc., such as waste paper pulp.

  The pulp is preferably a chemical pulp (sulfate pulp or sulfite pulp) with few impurities, and a pulp having a whiteness improved by bleaching is also useful.

  The freeness of the pulp used for papermaking is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is 24 mesh residual weight and 42 mesh fraction as defined in JIS P-8207. 30 to 70% of the sum with the weight% of is preferable. In addition, it is preferable that the weight% of 4 mesh remainder is 20 weight% or less.

Additives used for papermaking are conventionally known additives such as white pigments (calcium carbonate, talc, titanium oxide, etc.), binders, sizing agents (higher fatty acids, alkyl ketene dimers, etc.), softening agents (4 Grade ammonium), fixing agents, cationic agents, paper strength enhancers (starch, polyacrylamide, polyvinyl alcohol, etc.), water retention agents (polyethylene glycols, etc.) and the like.
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 . The support can also be given a high smoothness by calendering at the paper making stage or after paper making. The support density is generally 0.7 to 1.2 g / m ² (JIS P-8118). Furthermore, the support stiffness is preferably 20 to 200 g under the conditions specified in JIS P-8143.

The image receiving layer and the back layer may be provided on the support as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, an image receiving layer and a back layer may be provided to form an image receiving material. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
The support may be paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polybutene and copolymers thereof) or polyethylene terephthalate. White pigments (eg, titanium oxide, zinc oxide) or tinting dyes (eg, cobalt blue, ultramarine blue, neodymium oxide) may be added to the polyolefin.

  The image receiving layer provided on the support may contain a porous material or an aqueous binder. The image 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 image receiving layer include JP-A Nos. 10-81064, 10-119423, 10-157277, 10-217601, 11-348409, and JP-A-2001-138621. 2000-43401, 2000-2111235, 2000-309157, 2001-96897, 2001-138627, JP-A-11-91242, 8-2087, 8-2090, 8-2091, 8-9. 2093, 8-174992, 11-192777, JP-A-2001-301314, and the like can be used.

  The aqueous binder contained in the image receiving layer includes water-soluble polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, polyalkylene oxide derivatives, etc. Examples thereof include water-dispersible polymers such as 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 pigments and peel resistance of the image receiving layer.

  In addition to the above, the image-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.

The mordant added to the image 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. An image receiving 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 image 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 image receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. The image receiving layer may be one layer or two layers.

The support may be provided with a back layer. Examples of components that can be added to this layer include white pigments, aqueous binders, and other components.
Examples of white pigments contained in the back layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, white inorganic pigment, styrene Examples thereof include organic pigments such as plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin, and melamine resin.

  As the aqueous binder contained in the back layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, Examples thereof include water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the back layer include antifoaming agents, antifoaming agents, dyes, fluorescent whitening agents, preservatives, and water resistance agents.

  A polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the image receiving material. 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.

The ink-jet image receiving material of the present invention can be produced as follows.
That is, in the present invention, an inkjet image-receiving material is prepared by sizing an additive containing at least an organic mordant at the time of papermaking and / or sizing an additive containing at least an organic mordant after papermaking. Can be manufactured. Hereinafter, this production method will be described in detail.
The freeness (CSF) of the fibrous material used for the support is preferably 200 to 600 ml, more preferably 250 to 450 ml, from the balance of both dot shape and ink absorbency.
When the freeness (CSF) of the fiber material is low, the pore volume in the support is reduced to form a dense structure, and the outer pore diameter distribution is also shifted to a smaller one. That is, in the surface area of the image receiving material, the diameter of the depression or pore existing in the surface layer is reduced. For this reason, since the penetration of the ink droplet proceeds at almost the same speed in each direction, the dot shape is improved, but the penetration speed is slowed down, so-called the ink absorption speed is lowered. On the other hand, when the freeness (CSF) is high, an increase in pore volume and an average diameter in the image receiving material are observed, and although the ink absorption speed increases, the ink penetrates the image receiving material through the pores. The difference in permeation speed increases and the dot shape tends to be far from a perfect circle.

In the ink-jet image receiving material of the present invention, the additive used in papermaking is also important, and as the additive, it is preferable to use an inorganic compound having a predetermined characteristic value, particularly light calcium carbonate or synthetic silica. Is preferably used.
The specific surface area (S _BET ) of light calcium carbonate by the BET method is preferably 6 m ² / g or more, more preferably 6 to 30 m ² / g, and the S _BET of synthetic silica is preferably 100 m ² / g or more. Preferably it is 100-300 m < ² > / g. When the S _BET is too large, the weather resistance of the dots is lowered, and when the S _BET is too small, the liquid absorption characteristics are inferior. Incidentally, the larger the S _BET , the more uniformly the permeation of the ink receiving material surface in the ink receiving material surface in each direction, so that the dot shape becomes closer to a perfect circle.
When the inorganic compound has a large solid surface energy, a small contact angle with water, and the inner area of the particle has a large space or surface area that can adsorb water between the particles, the filling rate of the inorganic compound is high. Although the ink absorption rate is higher and the dot bleeding rate is lower, the image receiving material induces a decrease in mechanical strength. Therefore, in general, the filling rate of the inorganic compound is controlled to a certain amount or less in consideration of the balance between the optical properties such as whiteness and opacity of the image receiving material and the mechanical strength. On the other hand, when the filling rate of the inorganic compound is lowered, the ink absorption rate is lowered and the dot diameter is increased, thereby deteriorating the image receiving ability, but the influence of the decrease in mechanical strength is reduced. Therefore, in consideration of the balance between these properties and printing characteristics, the filling rate of the inorganic compound is preferably 10 to 16% by weight, more preferably 12 to 16% by weight, based on the fiber material in the case of light calcium carbonate. In the case of synthetic silica, it is preferably 5 to 15% by weight, more preferably 7 to 12% by weight, based on the fiber material.

The ink-jet image receiving material of the present invention is prepared by first adding a fiber material and an additive (which may or may not contain an organic mordant) to prepare a stock, and then making a paper by a conventional method. You may manufacture by sizing the additive as an agent. Here, sizing means that the additive is attached to at least the surface of the image receiving material, and a size press is usually used.
Examples of the sizing agent used in the paper stock include alkyl ketene dimer sizing agent, alkenyl succinic anhydride sizing agent and cationized petroleum resin sizing agent, which are generally called neutral sizing agents. It is preferable to add -1.5 mass%.
Examples of the sizing agent include styrene-acrylic acid copolymer, styrene-maleic acid copolymer, alkyl ketene dimer, petroleum resin, and polyacrylamide. The additive for sizing includes a film forming agent as necessary. Any one of various starches, polyvinyl alcohol and CMC or a mixture thereof can be added. In addition, cationic epoxy resin, polyallylamine, polyamine sulfone, dye fixing agent, polyamide epichlorohydrin, polyamine, alkylamine, polyallylamine hydrochloride, alkali metal chloride to enhance the water resistance and light resistance of recorded character images The object can be used in combination so as to adhere 1 g or less per 1 m ² of the image receiving material.
Betaine compound for use in the sizing is preferably 0.001 to 10 g / m ^2, more preferably 0.01-5 g / m ^2.
The amount of the sizing agent used for sizing is about 0.2 × 10 ^{−2 to} 3 × 10 ⁻² g / m ² when light calcium carbonate is used as the inorganic compound, and when synthetic silica is used as the inorganic compound. Is suitably about 0.2 to 3 g / m ² .
As described above, the sizing image receiving material has a Steecht sizing degree of 10 seconds or more, particularly 10 to 50 seconds, and can suppress the bleeding of the received ink and reduce the dot diameter. Since the agent is uniformly distributed, bleeding is suppressed and the shape and size of the dots are also stabilized. The Steecht sizing degree is based on the measurement method defined in JIS P8122.

The thickness of the ink-jet image receiving material of the present invention obtained as described above can be adjusted by a conventional method such as adjusting the fiber substance concentration in the paper stock, but the smoothness is moderately adjusted by a calendar roll. It may be adjusted to do. However, if the smoothness is too high, the dot shape may be adversely affected.
The smoothness of the ink-jet image receiving material of the present invention is preferably adjusted to 10 seconds to 80 seconds / ml. Here, the smoothness is measured according to JAPAN TAPPI Paper Pulp Test Method No. 5, m-74.

  As the image receiving material, for example, it can be used for display image materials, interior decoration materials, outdoor decoration materials, and the like.

  Display image materials include posters, wallpaper, small decorative items (such as figurines and dolls), commercial flyers, wrapping paper, wrapping materials, paper bags, plastic bags, packaging materials, signs, transportation (automobiles, buses, trains, etc.) ) Side materials, clothes with logos, etc.

  The interior decoration material refers to various items such as wallpaper, decorative accessories (such as figurines and dolls), lighting fixture members, furniture members, floor and ceiling design members.

  The outdoor decoration material refers to various materials such as wall materials, roofing materials, signboards, gardening materials, outdoor decoration accessories (such as figurines and dolls), and members of outdoor lighting equipment.

  In the applications as described above, examples of media on which an image is formed include various materials such as paper, fiber, cloth (including non-woven fabric), plastic, metal, ceramics, and combinations thereof. As the dyeing form, the dye can be fixed in the form of mordanting, printing, or a reactive dye having a reactive group introduced. Among these, it is preferable that the mordanting is performed.

The image receiving material of the present invention can be suitably used in an ink jet recording method in which ink droplets are ejected according to a recording signal and an image is recorded on the image receiving material.
There is no limitation on the ink jet recording method applied to the image receiving material of the present invention, and a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method that uses vibration pressure of a piezo element (Pressure pulse method), acoustic ink jet method that converts electrical signal into acoustic beam, irradiates ink and ejects ink using radiation pressure, and thermal that uses ink to form bubbles by heating ink Used in ink jet (bubble jet) systems.
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 present invention, the ejection frequency when ink is ejected onto the image receiving material is preferably 1 kHz or higher.
In order to record a high-quality image like a photograph, it is necessary to set the droplet ejection density to 600 dpi (number of dots per inch) or more in order to reproduce a sharp image with small ink droplets.
On the other hand, when ink is ejected by a head having a plurality of nozzles, in the type in which the image receiving material and the head move and record in a direction orthogonal to each other, the number of heads that can be driven simultaneously is about several tens to 200. There is a restriction that there are several hundreds even if the head is called a fixed type. This is because there are restrictions on driving power, and heat generated by the head affects the image, so that a large number of head nozzles cannot be driven simultaneously.
Here, the recording speed can be increased by increasing the drive frequency.
In the case of the thermal ink jet method, the droplet ejection frequency can be controlled by controlling the frequency of the head drive signal for heating the head.
In the case of the piezo method, this is possible by controlling the frequency of a signal for driving the piezo.
The driving of the piezo head will be described. For the image signal to be printed, the droplet size, droplet ejection speed, and droplet ejection frequency are determined by the printer control unit, and a signal for driving the print head is created. The drive signal is supplied to the print head. The droplet ejection size, droplet ejection speed, and droplet ejection frequency are controlled by a signal for driving the epizo. Here, the droplet ejection size and droplet ejection speed are determined by the shape and amplitude of the drive waveform, and the frequency is determined by the signal repetition period.
When this droplet ejection frequency is set to 10 KHz, the head is driven every 100 microseconds, and recording of one line is completed in 400 microseconds. By setting the moving speed of the recording paper to move 1/600 inch in 400 microseconds, that is, approximately 42 microns, it is possible to print at a speed of one sheet in 1.2 seconds.

With respect to the configuration of the printing apparatus to which the ink jet ink set is applied and the configuration of the printer, for example, a mode as disclosed in JP-A-11-170527 is preferable. As the ink cartridge, for example, the one disclosed in JP-A-5-229133 is suitable. With respect to the suction and the configuration of a cap or the like that covers the print head at that time, for example, the one disclosed in JP-A-7-276671 is suitable. Further, it is preferable that a filter for eliminating bubbles as disclosed in JP-A-9-277552 is provided in the vicinity of the head.
The surface of the nozzle is preferably subjected to water repellent treatment as described in Japanese Patent Application No. 2001-016738. The application may be a printer connected to a computer or an apparatus specialized for printing photographs.
The ink jet recording method of the present invention has an average droplet ejection speed of 2 m / sec or more when ejecting an ink obtained by dissolving and / or dispersing at least one dye in an aqueous medium onto an image receiving material, preferably It is preferably 5 m / sec or more.
The droplet ejection speed can be controlled by controlling the shape and amplitude of the waveform for driving 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.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

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) 7.5 g / l
Urea (UR) 10g / l
Proxel 5g / l
(Liquid component)
Diethylene glycol (DEG) 90g / l
Glycerin (GR) 70g / l
Triethylene glycol monobutyl ether (TGB) 70g / l
Triethanolamine (TEA) 6.9g / l
Surfynol STG (SW) 10g / l
[Magenta ink prescription]
(Solid content)
Magenta dye (M-1) 23g / l
Urea (UR) 15g / l
Proxel 5g / l
(Liquid component)
Diethylene glycol 90g / l
Glycerin 70g / l
Triethylene glycol monobutyl ether 70g / l
Triethanolamine 6.9g / 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) 115g / 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 108 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 number of anionic dissociation groups of the dye used is 4 for C-1, M-1, and BL-1, and 5 for Y-1 and BK-2.

In the table:
POEP-1: Polyoxyethylene nonylphenyl ether (PEO chain average 30)
POEN-1: Polyoxyethylene naphthyl ether (PEO chain average 50)
These inks are loaded into the ink cartridge of the EPSON ink jet printer PM-980C, and a single-color image of characters printed in C, M, Y, B, G, and R, and the center of a 3cm x 3cm color patch A pattern with a white background of the mold was printed.
The image-receiving sheet used here was a copy paper manufactured by FUJI XEROX for copying.
For image bleeding under high humidity conditions, this image sample printed on Fuji Photo Film Co., Ltd. inkjet paper photo glossy paper “Image Aya” is used at 25 ° C 90% RH. The test was carried out by storing for 20 hours under the above conditions.
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 ○.
For samples printed on copy paper, water drops were sprayed on the vertically hung image samples, and those that became impossible to interpret the characters were evaluated as “x”, and those that were sufficiently readable were rated as “◯”.
The results are shown below.

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

Claims (7)

  An ink-jet ink comprising at least a water-soluble dye having an anion-dissociating group, water and / or a water-miscible organic solvent, wherein at least a water-soluble organic compound having a cationic group capable of forming an ion pair with the anion-dissociating group 1 type of inkjet ink characterized by containing.   The inkjet ink according to claim 1, wherein the number of anion dissociation groups in one molecule of the dye is 3 or more.   The inkjet ink according to claim 1 or 2, wherein at least one of the anion dissociation groups is a sulfo group.   The ink-jet ink according to claim 1, wherein the water-soluble organic compound having a cationic group is a betaine compound.   The inkjet ink according to any one of claims 1 to 3, wherein the water-soluble organic compound having a cationic group is a water-soluble polymer obtained by polymerizing at least a monomer unit containing an amine nitrogen atom. .   An inkjet ink set comprising at least one ink according to any one of claims 1 to 5.   An ink jet recording method comprising: recording an image on plain paper by an ink jet printer using at least one of the inks or ink sets according to claim 1.