JP6108110B2 - Inkjet recording apparatus, inkjet recording method, recorded matter, and composite black - Google Patents

Description

  The present invention relates to an ink jet recording apparatus, an ink jet recording method, a recorded matter, and composite black.

  A water-based ink set for ink jet recording (hereinafter sometimes referred to as “water-based ink set” or “ink set”) is generally required to have excellent fastness to light, ozone, and the like. As an aqueous ink set excellent in fastness to light, ozone, etc., an aqueous ink set including an aqueous ink using a specific dye has been proposed (Patent Document 1).

JP 2011-111611 A

  However, some of the specific dyes are more likely to change in the ease of diffusion to the recording medium due to changes in environmental conditions of use than general dyes. For example, humidity affects the ease of diffusion of the specific dye into the recording medium. For this reason, for example, when the aqueous magenta ink containing the specific dye is mixed with the aqueous yellow ink and the aqueous cyan ink on the recording medium to record composite black (also referred to as tricolor black or process black), the high In a humid environment, the magenta color tone in the composite black becomes weak due to diffusion of the specific dye, and achromatic colors (for example, colors in the gradation range from black (black) to gray (gray)) are tinged with green. It may look like Further, composite black recorded on a recording medium is also required to have excellent fixability.

  Accordingly, an object of the present invention is to provide an ink jet recording apparatus, an ink jet recording method, and a recorded matter that can suppress the color change of the composite black and have excellent fixability. Another object of the present invention is to provide a composite black that can suppress color change and has excellent fixability.

式（Ｙ−１）において、
Ｒ_１、Ｒ_２、Ｙ_１及びＹ_２は、それぞれ、一価の基であり、Ｒ_１、Ｒ_２、Ｙ_１及びＹ_２は同一でも異なっていてもよく、
Ｘ_１及びＸ_２は、それぞれ、電子吸引性基であり、Ｘ_１及びＸ_２は同一でも異なっていてもよく、
Ｚ_１及びＺ_２は、それぞれ、水素原子、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、置換又は無置換のアルキニル基、置換又は無置換のアリール基、置換又は無置換のヘテロ環基であり、Ｚ_１及びＺ_２は同一でも異なっていてもよく、
Ｍ_１は、水素原子、アルカリ金属原子、ＮＨ_４又はＮＲ_４（Ｒは、アルキル基又はアリール基）である。

式（Ｍ−１）において、
ｎ_１は、１又は２であり、
３つのＭは、それぞれ、ナトリウム又はＮＨ_４であり、３つのＭは同一でも異なっていてもよく、
Ｒ_０は、カルボキシ基で置換された炭素原子数１〜８のモノアルキルアミノ基である。

式（Ｍ−２ａ）において、
Ｒ_１１は、水素原子、置換又は無置換のアルキル基、置換又は無置換のアリール基であり、
Ｒ_１２は、水素原子、ハロゲン原子又はシアノ基であり、
Ｒ_１３は、水素原子、置換又は無置換のアルキル基、置換又は無置換のアリール基、置換又は無置換のヘテロ環基であり、
Ｒ_１４、Ｒ_１５、Ｒ_１６及びＲ_１７は、それぞれ、水素原子、置換又は無置換のアルキル基、置換又は無置換のアリール基、置換又は無置換のヘテロ環基、置換又は無置換のスルホニル基、置換又は無置換のアシル基であり、Ｒ_１４、Ｒ_１５、Ｒ_１６及びＲ_１７は同一でも異なっていてもよいが、Ｒ_１４とＲ_１５が共に水素原子であることはなく、Ｒ_１６とＲ_１７が共に水素原子であることはなく、
Ａ_１及びＡ_２は、双方が置換又は無置換の炭素原子であるか、若しくは一方が置換又は無置換の炭素原子であり、かつ、他方が炭素原子である。

式（Ｍ−２ｂ）において、
ｒは、０、１又は２であり、
Ｒ_１８、Ｒ_１９及びＲ_２０は、それぞれ、置換又は無置換のアルキル基、置換又は無置換のアルコキシ基、ハロゲン原子、水素原子、ヒドロキシル基、置換又は無置換のカルバモイル基、置換又は無置換のスルファモイル基、置換又は無置換のアミノ基、ニトロ基、スルホン酸エステル基、置換又は無置換のアルキルスルホニル基、置換又は無置換のアリールスルホニル基、カルボキシ基、カルボン酸エステル基であり、Ｒ_１８、Ｒ_１９及びＲ_２０は同一でも異なっていてもよく、
Ｒ_２１、Ｒ_２２及びＲ_２３は、それぞれ、水素原子、置換又は無置換のアルキル基、置換又は無置換のアルケニル基、置換又は無置換のアリール基、置換又は無置換の脂環基、置換又は無置換のヘテロ環基であり、Ｒ_２１、Ｒ_２２及びＲ_２３は同一でも異なっていてもよい。

式（Ｃ−１）において、
環Ａ_３１、Ａ_３２及びＡ_３３は、それぞれ、ベンゼン環、２，３−ピリジン環及び３，２−ピリジン環からなる群から選択される少なくとも一つであり、かつ、環Ａ_３１、Ａ_３２及びＡ_３３の少なくとも一つは、２，３−ピリジン環又は３，２−ピリジン環であり、環Ａ_３１、Ａ_３２及びＡ_３３は同一でも異なっていてもよく、
ａは、０≦ａ≦４を満たし、ｂは、０≦ｂ≦４を満たし、ｃは、０≦ｃ≦４を満たし、かつ、ａ、ｂ及びｃは、０≦ａ＋ｂ＋ｃ≦４を満たし、
ｚは、１≦ｚ≦３を満たす整数であり、
Ｒ_３０は、炭素原子数１〜６の直鎖アルキレン基である。 In order to achieve the above object, an inkjet recording apparatus of the present invention comprises:
Including an ink container and an ink discharge means,
An ink jet recording apparatus capable of storing the following aqueous yellow ink, aqueous magenta ink, and aqueous cyan ink in the ink storage unit,
And further includes a control means,
The control means controls the ink ejection means so as to satisfy the following conditions (A) and (B) to form composite black on glossy paper.

(A) 0.68 ≦ M / (Y + C)
(B) 500 ≦ Y + M + C ≦ 600
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following yellow dye (Y-1) and yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following magenta dye (M-1) and magenta dye (M-2)
C: Drip amount (ng) per glossy paper 25.4 mm × 25.4 mm of the following cyan dye (C-1)

Water-based yellow ink: Water-based ink containing the following yellow dye (Y-1) and yellow dye (Y-2) Water-based magenta ink: Water-based ink aqueous cyan containing the following magenta dye (M-1) and magenta dye (M-2) Ink: Water-based ink containing the following cyan dye (C-1)

Yellow dye (Y-1): Dye represented by formula (Y-1) Yellow dye (Y-2): C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132 and C.I. I. At least one dye selected from the group consisting of Direct Yellow 142

Magenta dye (M-1): Dye represented by formula (M-1) Magenta dye (M-2): Dye represented by formula (M-2a), Dye represented by formula (M-2b) , C.I. I. Acid Red 1 and C.I. I. At least one dye selected from the group consisting of Acid Red 254

Cyan dye (C-1): Dye represented by formula (C-1)

In the formula (Y-1),
R ₁ , R ₂ , Y ₁ and Y ₂ are each a monovalent group, and R ₁ , R ₂ , Y ₁ and Y ₂ may be the same or different,
X ₁ and X ₂ are each an electron-withdrawing group, and X ₁ and X ₂ may be the same or different,
Z ₁ and Z ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, A cyclic group, Z ₁ and Z ₂ may be the same or different;
M ₁ is a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group).

In the formula (M-1),
n ₁ is 1 or 2,
The three M's are each sodium or NH ₄ , and the three M's may be the same or different;
R ₀ is a monoalkylamino group having 1 to 8 carbon atoms substituted with a carboxy group.

In the formula (M-2a),
R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
R ₁₂ is a hydrogen atom, a halogen atom or a cyano group,
R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted sulfonyl group. A substituted or unsubstituted acyl group, and R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different, but R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ is not both a hydrogen atom,
A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one is a substituted or unsubstituted carbon atom and the other is a carbon atom.

In formula (M-2b),
r is 0, 1 or 2;
R ₁₈ , R ₁₉ and R ₂₀ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. A sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a carboxy group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, substituted or unsubstituted It is an unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.

In formula (C-1),
Rings A ₃₁ , A ₃₂ and A ₃₃ are at least one selected from the group consisting of a benzene ring, a 2,3-pyridine ring and a 3,2-pyridine ring, respectively, and the rings A ₃₁ , A ₃₂ And at least one of A ₃₃ is a 2,3-pyridine ring or a 3,2-pyridine ring, and the rings A ₃₁ , A ₃₂ and A ₃₃ may be the same or different,
a satisfies 0 ≦ a ≦ 4, b satisfies 0 ≦ b ≦ 4, c satisfies 0 ≦ c ≦ 4, and a, b, and c satisfy 0 ≦ a + b + c ≦ 4,
z is an integer satisfying 1 ≦ z ≦ 3,
R ₃₀ is a linear alkylene group having 1 to 6 carbon atoms.

The inkjet recording method of the present invention comprises:
An inkjet recording method for recording using the water-based yellow ink, water-based magenta ink, and water-based cyan ink,
Composite black is formed on glossy paper so as to satisfy the conditions (A) and (B).

  The recorded matter of the present invention is recorded by the ink jet recording method of the present invention.

  The composite black of the present invention is characterized in that it is formed on glossy paper using the water-based yellow ink, water-based magenta ink, and water-based cyan ink so as to satisfy the conditions (A) and (B).

  According to the present invention, the specific yellow dye, magenta dye and cyan dye dripped onto the predetermined area of the glossy paper are controlled so as to satisfy the conditions (A) and (B). Can be suppressed, and the fixing property is also excellent.

FIG. 1A is a flowchart showing an example of formation of composite black in the present invention, and FIG. 1B shows an ink cartridge (ink storage portion) and an ink jet head (ink ejection means) of the ink jet recording apparatus of the present invention. ) And the control means. FIG. 2 is a schematic perspective view showing an example of the configuration of the ink jet recording apparatus of the present invention.

  In the present invention, “glossy paper” means, for example, a recording paper having at least one coating layer on the recording surface. Examples of the glossy paper include, for example, photographic glossy papers BP61G and BP71G manufactured by Brother Industries, Ltd .; inkjet paper painting photo finishing pro manufactured by FUJIFILM Corporation; high-grade glossy paper PWRA4-20 manufactured by Kodak Co., Ltd. And so on.

  As described above, in the ink jet recording apparatus and the ink jet recording method of the present invention, recording is performed using the water-based yellow ink, water-based magenta ink, and water-based cyan ink.

(Water-based yellow ink)
As described above, the water-based yellow ink includes the yellow dye (Y-1) and the yellow dye (Y-2).

  As described above, the yellow dye (Y-1) is a dye represented by the formula (Y-1).

In the formula (Y-1), R ₁ , R ₂ , Y ₁ and Y ₂ are each a monovalent group, and R ₁ , R ₂ , Y ₁ and Y ₂ may be the same or different. The monovalent group is a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include a halogen atom; an alkyl group; a cycloalkyl group; an aralkyl group; an alkenyl group; an alkynyl group; an aryl group; a heterocyclic group; a cyano group; a hydroxyl group; Oxy group; silyloxy group; heterocyclic oxy group; acyloxy group; carbamoyloxy group; alkoxycarbonyloxy group; aryloxycarbonyloxy group; amino group such as alkylamino group and arylamino group; amide group; acylamino group; Alkoxycarbonylamino group; aryloxycarbonylamino group; sulfamoylamino group; alkylsulfonylamino group; arylsulfonylamino group; alkylthio group; arylthio group; heterocyclic thio group; Alkylsulfonyl group; arylsulfonyl group; acylsulfonyl; aryloxycarbonyl group; alkoxycarbonyl group; carbamoyl group; phosphino group; phosphinyloxy group; phosphinyloxy group; And silyl group; azo group; imide group and the like. The monovalent substituent may further have a substituent. Among these, preferable monovalent substituents are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group. , A sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, and an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, and an alkylsulfonyl group.

  In the formula (Y-1), the halogen atom is a chlorine atom, a bromine atom or an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.

  In the formula (Y-1), the alkyl group includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group, a tert-butyl group, an n-octyl group, an eicoxy group, a 2-chloroethyl group, a hydroxyethyl group, a cyanoethyl group, and a 4-sulfobutyl group. . Examples of the substituent of the substituted alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 2-methylsulfonylethyl group, 3- A linear or branched alkyl group having 1 to 12 carbon atoms such as a phenoxypropyl group or a trifluoromethyl group; a linear or branched aralkyl group having 7 to 18 carbon atoms; a linear chain having 2 to 12 carbon atoms or A branched alkenyl group; a linear or branched alkynyl group having 2 to 12 carbon atoms; a linear or branched cycloalkyl group having 3 to 12 carbon atoms such as a cyclopentyl group; a linear chain having 3 to 12 carbon atoms or Branched cycloalkenyl group; halogen atom such as chlorine atom and bromine atom; phenyl group, 4-tert-butylphenyl group, 2,4-di-tert-amylphenyl group A heterocyclic group such as imidazolyl group, pyrazolyl group, triazolyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group; cyano group; hydroxyl group; nitro group; carboxy group; Amino group; alkoxy group such as methoxy group, ethoxy group, 2-methoxyethoxy group, 2-methylsulfonylethoxy group; phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 3 Aryloxy groups such as tert-butyloxycarbonylphenoxy group and 3-methoxycarbonylphenyloxy group; acylamino groups such as acetamido group, benzamide group and 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide group; methyl Amino group, butylamino group, di Alkylamino groups such as tilamino group and methylbutylamino group; arylamino groups such as phenylamino group and 2-chloroanilino group; ureido groups such as phenylureido group, methylureido group and N, N-dibutylureido group; N, N -Sulfamoylamino group such as dipropylsulfamoylamino group; alkylthio group such as methylthio group, octylthio group, 2-phenoxyethylthio group; phenylthio group, 2-butoxy-5-tert-octylphenylthio group, 2- Arylthio groups such as carboxyphenylthio group; alkoxycarbonylamino groups such as methoxycarbonylamino group; alkylsulfonylamino groups such as methylsulfonylamino group; arylsulfonylamino groups such as phenylsulfonylamino group and p-toluenesulfonylamino group; N − Carbamoyl groups such as ethylcarbamoyl group and N, N-dibutylcarbamoyl group; sulfamoyl groups such as N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group and N-phenylsulfamoyl group; methylsulfonyl group; Sulfonyl groups such as octylsulfonyl group, phenylsulfonyl group and p-toluenesulfonyl group; alkoxycarbonyl groups such as methoxycarbonyl group and butyloxycarbonyl group; 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group and the like A heterocyclic oxy group; an azo group such as a phenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group; an acyloxy group such as an acetoxy group; N -Phenylcarbamoyloxy group, etc. Rubamoyloxy group; silyloxy group such as trimethylsilyloxy group and dibutylmethylsilyloxy group; aryloxycarbonylamino group such as phenoxycarbonylamino group; imide group such as N-succinimide group and N-phthalimide group; 2-benzothiazolylthio group , 2,4-di-phenoxy-1,3,5-triazole-6-thio group, heterocyclic thio group such as 2-pyridylthio group; sulfinyl group such as 3-phenoxypropylsulfinyl group; phenoxyphosphonyl group, octyl Phosphonyl groups such as oxyphosphonyl group and phenylphosphonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acyl groups such as acetyl group, 3-phenylpropanoyl group and benzoyl group; carboxy group, sulfo group, phosphono group, Quaternary ammonium group, etc. Such an ionic hydrophilic group. The alkyl group, the aralkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, and the cycloalkenyl group, which are substituents of the substituted alkyl group, improve dye solubility and aqueous yellow ink stability. From the viewpoint, those having a branched chain are preferred, and those having an asymmetric carbon are particularly preferred. Among these, preferred substituents of the substituted alkyl group are a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt), and a carboxy group (may be in the form of a salt).

  In the formula (Y-1), the cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent of the substituted cycloalkyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and 4-n-dodecylcyclohexyl group.

  In the formula (Y-1), the aralkyl group includes a substituted or unsubstituted aralkyl group. The substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent of the substituted aralkyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the aralkyl group include benzyl group and 2-phenethyl group.

  In the formula (Y-1), the alkenyl group is a linear, branched or cyclic substituted or unsubstituted alkenyl group. The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. Examples of the substituent of the substituted alkenyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkenyl group include a vinyl group, allyl group, prenyl group, geranyl group, oleyl group, 2-cyclopenten-1-yl group, and cyclohexen-1-yl group.

  In the formula (Y-1), the alkynyl group is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms. Examples of the substituent of the substituted alkynyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkynyl group include ethynyl group and propargyl group.

  In the formula (Y-1), the aryl group is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of the aryl group include a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group, and the like. Examples of the substituent of the substituted aryl group include the same substituents as the substituents of the substituted alkyl group.

  In the formula (Y-1), the heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. , They may be further condensed. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent of the substituted heterocyclic group include the same substituents as the substituents of the substituted alkyl group. As the heterocyclic group, if the substitution position is not limited, for example, pyridine group, pyrazine group, pyridazine group, pyrimidine group, triazine group, quinoline group, isoquinoline group, quinazoline group, cinnoline group, phthalazine group, quinoxaline group, Pyrrole group, indole group, furan group, benzofuran group, thiophene group, benzothiophene group, pyrazole group, imidazole group, benzimidazole group, triazole group, oxazole group, benzoxazole group, thiazole group, benzothiazole group, isothiazole group, Examples thereof include a benzisothiazole group, a thiodiazole group, an isoxazole group, a benzisoxazole group, a pyrrolidine group, a piperidine group, a piperazine group, an imidazolidine group, and a thiazoline group.

  In the formula (Y-1), the alkoxy group includes a substituted or unsubstituted alkoxy group. The substituted or unsubstituted alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms. Examples of the substituent of the substituted alkoxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

  In the formula (Y-1), the aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent of the substituted aryloxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, and the like.

  In the formula (Y-1), the silyloxy group is preferably a silyloxy group having 3 to 20 carbon atoms. Examples of the silyloxy group include trimethylsilyloxy group and tert-butyldimethylsilyloxy group.

  In the formula (Y-1), the heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent of the substituted heterocyclic oxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group and the like.

  In the formula (Y-1), the acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted aryl having 6 to 30 carbon atoms. A carbonyloxy group; Examples of the substituent of the substituted alkylcarbonyloxy group and the substituted arylcarbonyloxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.

  In the formula (Y-1), the carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of the substituent of the substituted carbamoyloxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the carbamoyloxy group include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn- Examples include octylcarbamoyloxy group.

  In the formula (Y-1), the alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the substituent of the substituted alkoxycarbonyloxy group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

  In the formula (Y-1), the aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the substituent for the aryloxycarbonyloxy group include the same substituents as the substituents for the substituted alkyl group. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a pn-hexadecyloxyphenoxycarbonyloxy group, and the like.

  In the formula (Y-1), the amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of the substituent of the substituted alkylamino group and the substituted arylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the amino group include amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, hydroxyethylamino group, carboxyethylamino group, sulfoethylamino group, 3 , 5-dicarboxyanilino group and the like.

  In the formula (Y-1), the acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl having 6 to 30 carbon atoms. A carbonylamino group. Examples of the substituent of the substituted alkylcarbonylamino group and the substituted arylcarbonylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  In the formula (Y-1), the aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the substituent of the substituted aminocarbonylamino group include: And the same substituents as the substituents for the substituted alkyl group. Examples of the aminocarbonylamino group include carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, and the like.

  In the formula (Y-1), the alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent of the substituted alkoxycarbonylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.

  In the formula (Y-1), the aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the substituent of the substituted aryloxycarbonylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, and the like.

  In the formula (Y-1), the sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the substituent of the substituted sulfamoylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the sulfamoylamino group include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.

  In the formula (Y-1), the alkylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms. Examples of the substituent of the substituted alkylsulfonylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkylsulfonylamino group include a methylsulfonylamino group and a butylsulfonylamino group.

  In the formula (Y-1), the arylsulfonylamino group is preferably a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms. Examples of the substituent of the substituted arylsulfonylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the arylsulfonylamino group include a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, and the like.

  In the formula (Y-1), the alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the substituent of the substituted alkylthio group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexylthio group.

  In the formula (Y-1), the arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. Examples of the substituent for the substituted arylthio group include the same substituents as the substituents for the substituted alkyl group. Examples of the arylthio group include a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  In the formula (Y-1), the heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent of the substituted heterocyclic thio group include the same substituents as the substituents of the substituted alkyl group. Examples of the heterocyclic thio group include 2-benzothiazolylthio group and 1-phenyltetrazol-5-ylthio group.

  In the formula (Y-1), the sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the substituent of the substituted sulfamoyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the sulfamoyl group include an N-ethylsulfamoyl group, an N- (3-dodecyloxypropyl) sulfamoyl group, an N, N-dimethylsulfamoyl group, an N-acetylsulfamoyl group, and an N-benzoylsulfur group. Examples include a famoyl group and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  In the formula (Y-1), the alkylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms. Examples of the substituent of the substituted alkylsulfinyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkylsulfinyl group include a methylsulfinyl group and an ethylsulfinyl group.

  In the formula (Y-1), the arylsulfinyl group is preferably a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. Examples of the substituent of the substituted arylsulfinyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the arylsulfinyl group include a phenylsulfinyl group and a p-methylsulfinyl group.

  In the formula (Y-1), the alkylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms. Examples of the substituent of the substituted alkylsulfonyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.

  In the formula (Y-1), the arylsulfonyl group is preferably a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. Examples of the substituent of the substituted arylsulfonyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the arylsulfonyl group include a phenylsulfonyl group and a p-toluenesulfonyl group.

  In the formula (Y-1), the acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms. , A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. Examples of the substituent of the substituted alkylcarbonyl group, the substituted arylcarbonyl group, and the substituted heterocyclic carbonyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the acyl group include an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxycarbonyl group, a 2-pyridylcarbonyl group, and a 2-furylcarbonyl group. .

  In the formula (Y-1), the aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the substituent of the aryloxycarbonyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, and a p-tert-butylphenoxycarbonyl group.

  In the formula (Y-1), the alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent of the substituted alkoxycarbonyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  In the formula (Y-1), the carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the substituent of the substituted carbamoyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the carbamoyl group include a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, and an N- (methylsulfonyl) carbamoyl group.

  In the formula (Y-1), the phosphino group is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. Examples of the substituent of the substituted phosphino group include the same substituents as the substituents of the substituted alkyl group. Examples of the phosphino group include a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group.

  In the formula (Y-1), the phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. Examples of the substituent of the substituted phosphinyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the phosphinyl group include a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  In the formula (Y-1), the phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examples of the substituent of the substituted phosphinyloxy group include the same substituents as the substituents of the alkyl group. Examples of the phosphinyloxy group include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  In the formula (Y-1), the phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. Examples of the substituent of the phosphinylamino group include the same substituents as the substituents of the substituted alkyl group. Examples of the phosphinylamino group include a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.

  In the formula (Y-1), the silyl group is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. Examples of the substituent of the substituted silyl group include the same substituents as the substituents of the substituted alkyl group. Examples of the silyl group include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a phenyldimethylsilyl group.

  In the formula (Y-1), examples of the azo group include phenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, and the like. It is done.

  In the formula (Y-1), examples of the imide group include an N-succinimide group and an N-phthalimide group.

In formula (Y-1), X ₁ and X ₂ are each an electron-withdrawing group, and X ₁ and X ₂ may be the same or different. Examples of X ₁ and X ₂ include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, a diarylphosphono group, and a diarylphosphinyl group. Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, Examples thereof include a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group, a heterocyclic group, a halogen atom, an azo group, and a selenocyanate group.

In the formula (Y-1), X ₁ and X ₂ are preferably an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, carbon An alkoxycarbonyl group having 2 to 12 atoms, an aryloxycarbonyl group having 7 to 18 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an arylsulfinyl group having 6 to 18 carbon atoms, An alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. A halogenated alkoxy group of 1 to 12 carbon atoms, a halogenated aryloxy group of 7 to 18 carbon atoms, 2 or more A 5- to 8-membered heterocyclic group having 1 to 18 carbon atoms having an aryl group having 7 to 18 carbon atoms, a nitrogen atom, an oxygen atom, or a sulfur atom substituted with another electron-withdrawing group .

In Formula (Y-1), Z ₁ and Z ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl. A group, a substituted or unsubstituted heterocyclic group, and Z ₁ and Z ₂ may be the same or different. The alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the heterocyclic group are the same as those in R ₁ , R ₂ , Y _1, and Y ₂ .

In Formula (Y-1), M ₁ is a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group). The alkali metal atom is preferably Li, Na, or K. The alkyl group or aryl group in R is the same as that in R ₁ , R ₂ , Y ₁ and Y ₂ . Among these, M ₁ is preferably Li, Na, K, NH ₄ .

  As a preferable combination of substituents of the dye represented by the formula (Y-1), it is preferable that at least one of the substituents is the above preferable group, and that more substituents are the above preferable group. More preferably, all substituents are most preferably the above preferred groups.

  Particularly preferred combinations of substituents of the dye represented by the formula (Y-1) include the following (a) to (e).

(I) R ₁ and R ₂ may be the same or different, and are preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted 6 to 18 carbon atoms. An aryl group, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms in total, and more preferably secondary. Or a tertiary alkyl group, and most preferably a tert-butyl group.

(B) X ₁ and X ₂ are each an electron-withdrawing group, and may be the same or different, and are preferably a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and 6 to 18 carbon atoms. And a sulfamoyl group having 0 to 12 carbon atoms, more preferably a cyano group and an alkylsulfonyl group having 1 to 12 carbon atoms.

(C) Y ₁ and Y ₂ may be the same or different, and are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 total carbon atoms, or a substituted or unsubstituted total carbon number of 6 An aryl group having 18 to 18 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, and most preferably a hydrogen atom. .

(D) Z ₁ and Z ₂ may be the same or different and are preferably a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms in total, or a substituted or unsubstituted total carbon atom having 6 to 18 carbon atoms. An aryl group, a substituted or unsubstituted heterocyclic group having 4 to 12 total carbon atoms, more preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and particularly preferably a substituted group. An aryl group.

(E) M ₁ is preferably a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group), more preferably a hydrogen atom, Li, Na, K, NH _4. It is.

  Preferable specific examples of the dye (Y-1) include compounds represented by the formulas (Y-1a) to (Y-1e).

  The blending amount of the yellow dye (Y-1) is not particularly limited. Inclusion of the yellow dye (Y-1) in the aqueous yellow ink can improve light resistance and ozone resistance. The blending amount of the yellow dye (Y-1) is, for example, 0.1% by weight to 10% by weight, preferably 1.2% by weight to 5.4% by weight, based on the total amount of the aqueous yellow ink. Yes, more preferably from 1.5 wt% to 4.5 wt%.

  As described above, the yellow dye (Y-2) is C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132 and C.I. I. It is at least one dye selected from the group consisting of direct yellow 142.

  C. I. Direct yellow 86 is, for example, a dye represented by the formula (Y-2a).

  C. I. The direct yellow 132 is a dye represented by the formula (Y-2b), for example.

  C. I. The direct yellow 142 is, for example, a dye represented by the formula (Y-2c).

  The blending amount of the yellow dye (Y-2) is not particularly limited. By including the yellow dye (Y-2) in the aqueous yellow ink, the storage stability can be improved. The blending amount of the yellow dye (Y-2) is, for example, 0.1 wt% to 10 wt%, preferably 0.2 wt% to 2.4 wt%, with respect to the total amount of the aqueous yellow ink. Yes, more preferably 0.4 wt% to 1.6 wt%.

  The weight ratio of the yellow dye (Y-1) to the yellow dye (Y-2) in the water-based yellow ink is yellow dye (Y-1): yellow dye (Y-2) = 60: 40 to 90: 10 is preferable. By setting the weight ratio within the above range, it is possible to obtain a water-based yellow ink having extremely good storage stability, light resistance, and ozone resistance.

  The total amount of the yellow dye (Y-1) and the yellow dye (Y-2) is not particularly limited, but is preferably 2% by weight to 6% by weight with respect to the total amount of the aqueous yellow ink. By setting the total blending amount within the above range, it is possible to obtain an aqueous yellow ink having all of storage stability, color developability, light resistance, ozone resistance and jetting stability.

  The water-based yellow ink may further contain another yellow colorant in addition to the yellow dye (Y-1) and the yellow dye (Y-2). Examples of the other yellow colorant include dyes and pigments other than the yellow dye (Y-1) and the yellow dye (Y-2).

  The water-based yellow ink may further contain water and a water-soluble organic solvent.

  The water is preferably ion exchange water or pure water. The blending amount (water ratio) of the water with respect to the total amount of the water-based yellow ink is, for example, 10% by weight to 90% by weight, and preferably 40% by weight to 80% by weight. The said water ratio is good also as the remainder of another component, for example.

  Examples of the water-soluble organic solvent include a wetting agent that prevents drying of the aqueous yellow ink at the nozzle tip of the ink jet head and a penetrating agent that adjusts the drying speed on the recording medium.

  The wetting agent is not particularly limited, and examples thereof include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; dimethylformamide, dimethylacetamide Amides such as acetone; Ketones such as acetone; Keto alcohols such as diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyethers such as polyalkylene glycol; Polyhydric alcohols such as alkylene glycol, glycerin and trimethylolpropane; 2-pyrrolidone; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone and the like. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, thiodiglycol, and hexylene glycol. These wetting agents may be used alone or in combination of two or more. Among these, polyhydric alcohols such as alkylene glycol and glycerin are preferable.

  The blending amount of the wetting agent with respect to the total amount of the water-based yellow ink is, for example, 0% by weight to 95% by weight, preferably 5% by weight to 80% by weight, and more preferably 5% by weight to 50% by weight. It is.

  Examples of the penetrant include glycol ether. Examples of the glycol ether include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol-n-propyl ether, diethylene glycol-n-butyl ether, diethylene glycol-n-. Hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol-n-propyl ether, triethylene glycol-n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol-n-propyl ether , Propylene glycol-n-butyl ether , Dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol-n-propyl ether And tripropylene glycol-n-butyl ether. The penetrant may be used alone or in combination of two or more.

  The blending amount of the penetrant with respect to the total amount of the aqueous yellow ink is, for example, 0% by weight to 20% by weight, preferably 0.1% by weight to 15% by weight, and more preferably 0.5% by weight. -10% by weight.

  The water-based yellow ink may further contain a conventionally known additive as required. Examples of the additive include a surfactant, a pH adjuster, a viscosity adjuster, a surface tension adjuster, and an antifungal agent. Examples of the viscosity modifier include polyvinyl alcohol, cellulose, and a water-soluble resin.

  The water-based yellow ink is prepared by, for example, uniformly mixing the yellow dye (Y-1) and the yellow dye (Y-2) with other additive components as necessary, using a conventionally known method, a filter, etc. To remove the insoluble matter.

(Water-based magenta ink)
As described above, the water-based magenta ink includes the magenta dye (M-1) and the magenta dye (M-2).

  As described above, the magenta dye (M-1) is a dye represented by the formula (M-1).

The compound represented by the formula (M-1) may be a compound (sodium salt) in which all three M are sodium, or may be a compound (ammonium salt) in which all three M are ammonium. Further, it may be a compound in which one or two of the three Ms are sodium and the rest are ammonium.
The magenta dye (M-1) may be composed of a single compound or a mixture containing two or more compounds.
The M may be ionized (at least one of Na ⁺ and NH ₄ ⁺ ) by ionization in an aqueous magenta ink.

  Preferable specific examples of the magenta dye (M-1) include compounds represented by magenta dyes (M-1a) to (M-1e) shown in Table 1.

  As described above, the magenta dye (M-2) is a dye represented by the formula (M-2a), a dye represented by the formula (M-2b), C.I. I. Acid Red 1 and C.I. I. It is at least one dye selected from the group consisting of Acid Red 254.

  In the formula (M-2a), the substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. Examples of the substituted or unsubstituted alkyl group include a methyl group, ethyl group, n-butyl group, isopropyl group, tert-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3- Examples thereof include a sulfopropyl group and a 4-sulfobutyl group. Examples of the substituent of the substituted alkyl group include hydroxyl group; alkoxy group such as methoxy group and ethoxy group; cyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxylate salt and sulfonic acid Examples thereof include ionic hydrophilic groups such as salts.

  In the formula (M-2a), the substituted or unsubstituted aryl group is preferably an aryl group having 6 to 12 carbon atoms. However, in the case of a substituted aryl group, the number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the substituted or unsubstituted aryl group include phenyl group, naphthyl group, p-tolyl group, p-octylphenyl group, mesityl group, p-methoxyphenyl group, o-chlorophenyl group, m- (3-sulfo group). Propylamino) phenyl group and the like. Examples of the substituent of the substituted aryl group include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an n-octyl group; an alkoxy group similar to the above; a halogen atom similar to the above; Alkylamino groups such as amino groups and dimethylamino groups; Amido groups; Carbamoyl groups; Sulfamoyl groups; Sulfamide groups; Hydroxyl groups; Ester groups such as methoxycarbonyl groups and ethoxycarbonyl groups; It is done.

  In the formula (M-2a), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the formula (M-2a), the substituted or unsubstituted heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituted or unsubstituted heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-furyl group, 6-sulfobenzothiazolyl group, 6- Examples thereof include a sulfonate benzothiazolyl group. Examples of the substituent of the substituted heterocyclic group include an amide group; a carbamoyl group; a sulfamoyl group; a sulfoamide group; a hydroxyl group; an ester group as described above; and an ionic hydrophilic group as described above.

  In the formula (M-2a), examples of the substituted or unsubstituted sulfonyl group include a methylsulfonyl group and a phenylsulfonyl group. Examples of the substituent of the substituted sulfonyl group include the same substituted or unsubstituted alkyl group as described above, and the same substituted or unsubstituted aryl group as described above.

  In the formula (M-2a), the substituted or unsubstituted acyl group is preferably an acyl group having 1 to 12 carbon atoms. However, in the case of a substituted acyl group, the number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the substituted or unsubstituted acyl group include an acetyl group, a benzoyl group, and a chloroacetyl group. Examples of the substituent of the substituted acyl group include the same ionic hydrophilic groups as described above.

In formula (M-2a), as described above, A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one is a substituted or unsubstituted carbon atom and the other is nitrogen. Is an atom. The case where both A ₁ and A ₂ are carbon atoms is preferable in that it can exhibit more excellent performance. Examples of the substituent bonded to the carbon atom of A ₁ and A _2, for example, an alkyl group having 1 to 3 carbon atoms, a carboxy group, a carbamoyl group, a cyano group, and the like.

As described above, in the formula (M-2a), R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ are not both hydrogen atoms. Moreover, in Formula (M-2a), when the number of substitutions of a sulfonic acid group or a carboxy group increases, the water solubility of the dye tends to be improved. Therefore, it is preferable to adjust the number of substitutions as necessary.

As a preferable aspect of the magenta dye (M-2a), for example, in the formula (M-2a), R ₁₁ is an alkyl group, R ₁₂ is a cyano group, R ₁₃ is a hydrogen atom or a substituted or unsubstituted heterocyclic group. , R ₁₄ is a hydrogen atom, a substituted or unsubstituted heterocyclic group or substituted aryl group, R ₁₅ and R ₁₆ are respectively a substituted heterocyclic group or a substituted aryl group, R ₁₇ is a hydrogen atom, and A ₁ is substituted. And the carbon atom A ₂ is a substituted or unsubstituted carbon atom.

As a more preferable embodiment of the magenta dye (M-2a), for example, in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ is a hydrogen atom or a sulfonic acid group or a group thereof. A benzothiazolyl group (preferably a benzothiazol-2-yl group) optionally substituted with an alkali metal base, R ₁₄ is a hydrogen atom, a sulfonic acid group or a benzothiazolyl group optionally substituted with an alkali metal base (preferably, Benzothiazol-2-yl group) or a trialkylphenyl group (preferably a mesityl group) substituted with a sulfonic acid group or an alkali metal base thereof, and R ₁₅ and R ₁₆ are a sulfonic acid group or an alkali metal thereof, respectively. Mono, di or trialkylphenyl groups which may be substituted with bases (preferably is a benzothiazolyl group (preferably substituted with p- octylphenyl group or a mesityl group) or a sulfonic acid group or alkali metal bases, benzothiazol-2-yl group), R ₁₇ is a hydrogen atom, A ₁ is a substituted In this embodiment, A ₂ is a carbon atom that may be substituted with a cyano group.

  Preferable specific examples of the magenta dye (M-2a) include compounds represented by formulas (M-2a-1) to (M-2a-6).

In the compound represented by the formula (M-2a-1), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ is a benzothiazol-2-yl group, R ₁₄ Is a hydrogen atom, R ₁₅ and R ₁₆ are each a p-octylphenyl group, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is substituted with a cyano group The embodiment is a carbon atom.

In the compound represented by the formula (M-2a-2), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are each benzothiazole-2 The yl group, R ₁₅ and R ₁₆ are each a mesityl group, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is a carbon atom.

In the compound represented by the formula (M-2a-3), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are each 6-sulfosodium. A salt benzothiazol-2-yl group, R ₁₅ and R ₁₆ are each a 3-sulfosodium salt mesityl group, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is The embodiment is a carbon atom.

In the compound represented by the formula (M-2a-4), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are each 6-sulfolithium. A salt benzothiazol-2-yl group, R ₁₅ and R ₁₆ are each a 2,6-diethyl-4-methyl-3-sulfolithium phenyl group, R ₁₇ is a hydrogen atom, and A ₁ is a methyl group carbon atoms which is substituted, a ₂ is a mode which is a carbon atom.

In the compound represented by the formula (M-2a-5), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are each 6-sulfopotassium. A salt benzothiazol-2-yl group, R ₁₅ and R ₁₆ are each a 3-sulfo potassium salt mesityl group, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is The embodiment is a carbon atom.

In the compound represented by the formula (M-2a-6), in the formula (M-2a), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are 6-sulfo lithium salt benzothiazole 2-yl group, R ₁₅ and R ₁₆ are 2,6-diethyl-4-sulfolithium phenyl groups, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is The embodiment is a carbon atom.

  When the magenta dye (M-2) is the magenta dye (M-2a), the magenta dye (M-1) is included in the water-based magenta ink so that light resistance, ozone resistance, and jetting stability are increased. Can be improved. The blending amount of the magenta dye (M-1) in this case is not particularly limited, but is, for example, 0.1 wt% to 10 wt%, preferably 0.4 wt%, based on the total amount of the aqueous magenta ink. % To 3.6% by weight, and more preferably 0.8% to 3% by weight.

  When the magenta dye (M-2) is the magenta dye (M-2a), the magenta dye (M-2) is included in the water-based magenta ink so that the coloring property, light resistance and ozone resistance are increased. Can be improved. The blending amount of the magenta dye (M-2) in this case is not particularly limited, but is, for example, 0.1% by weight to 10% by weight, preferably 0.8% by weight with respect to the total amount of the aqueous magenta ink. % To 4.8% by weight, and more preferably 1.0% to 3.2% by weight.

  When the magenta dye (M-2) is the magenta dye (M-2a), the weight ratio of the magenta dye (M-1) to the magenta dye (M-2) in the aqueous magenta ink is: Magenta dye (M-1): Magenta dye (M-2) = 60: 40 to 20:80 is preferable. By setting the weight ratio in the above range, it is possible to obtain a water-based magenta ink having both excellent color developability and jetting stability.

In the formula (M-2b), the substituted or unsubstituted alkyl group in R ₁₈ , R ₁₉ and R ₂₀ is preferably an alkyl group having 1 to 9 carbon atoms in total. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a trifluoromethyl group, and a dimethylaminomethyl group. Examples of the substituent of the substituted alkyl group include hydroxyl group; alkoxy group such as methoxy group and ethoxy group; cyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxylate salt and sulfonic acid Examples thereof include ionic hydrophilic groups such as salts.

In the formula (M-2b), the substituted or unsubstituted alkoxy group in R ₁₈ , R ₁₉ and R ₂₀ is preferably an alkoxy group having 1 to 9 carbon atoms in total. Examples of the substituted or unsubstituted alkoxy group include a methoxy group, an isopropoxy group, and an n-butoxy group.

In the formula (M-2b), examples of the halogen atom in R ₁₈ , R _19, and R ₂₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formula (M-2b), examples of the substituted or unsubstituted carbamoyl group in R ₁₈ , R ₁₉ and R ₂₀ include a carbamoyl group, an N, N-dimethylcarbamoyl group, and a phenylcarbamoyl group.

In the formula (M-2b), examples of the substituted or unsubstituted sulfamoyl group in R ₁₈ , R ₁₉ and R ₂₀ include a sulfamoyl group, an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N— Examples thereof include an ethyl-N-phenylsulfamoyl group, an N, N-dimethylsulfamoyl group, and a p-carboxyphenylsulfamoyl group.

In the formula (M-2b), examples of the substituted or unsubstituted amino group in R ₁₈ , R ₁₉ and R ₂₀ include an N-methylamino group, a carbamoylamino group, an N, N-diethylamino group, and an acetylamino group. Can be given.

In the formula (M-2b), examples of the sulfonate group in R ₁₈ , R ₁₉ and R ₂₀ include a phenoxysulfonyl group.

In formula (M-2b), the substituted or unsubstituted alkylsulfonyl group in R ₁₈ , R ₁₉ and R ₂₀ is preferably an alkylsulfonyl group having 1 to 9 carbon atoms in total. Examples of the substituted or unsubstituted alkylsulfonyl group include a hydroxysulfonyl group.

In formula (M-2b), the substituted or unsubstituted arylsulfonyl group in R ₁₈ , R ₁₉ and R ₂₀ is preferably an arylsulfonyl group having 6 to 15 carbon atoms in total. Examples of the substituted or unsubstituted arylsulfonyl group include a benzylsulfonyl group.

In the formula (M-2b), examples of the carboxylic acid ester group in R ₁₈ , R ₁₉ and R ₂₀ include a methoxycarbonyl group and the like.

In the formula (M-2b), the substituted or unsubstituted alkyl group in R ₂₁ , R ₂₂ and R ₂₃ is preferably an alkyl group having 1 to 18 carbon atoms in total. Examples of the substituted or unsubstituted alkyl group include an ethyl group, an n-butyl group, an n-octyl group, an ethylhexyl group, a hydroxyethyl group, a carboxypropyl group, a carboxycyclohexylmethyl group, and 1-carboxy-2-mercaptoethyl. Group, 1-carboxy-2-carbamoyl-ethyl group, 1-isopropyl-1-carboxymethyl group, 1,2-dicarboxypropyl group and the like. Examples of the substituent of the substituted alkyl group include hydroxyl group; alkoxy group such as methoxy group and ethoxy group; cyano group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxylate salt and sulfonic acid Examples thereof include ionic hydrophilic groups such as salts.

In the formula (M-2b), the substituted or unsubstituted alkenyl group in R ₂₁ , R ₂₂ and R ₂₃ is preferably an alkenyl group having 2 to 18 carbon atoms in total. Examples of the substituted or unsubstituted alkenyl group include 2-methyl-1-propenyl group, vinyl group, allyl group and the like.

In the formula (M-2b), examples of the substituted or unsubstituted aryl group in R ₂₁ , R ₂₂ and R ₂₃ include a 3,4-dicarboxyphenyl group, a 4-butylphenyl group, and a 4-carboxyphenyl group. Can be given. Examples of the substituent of the substituted aryl group include the same substituents as the substituent of the substituted alkyl group.

In the formula (M-2b), R ₂₁ , R ₂₂ and R ₂₃ are, for example, benzyl group, 1-carboxy-2-phenyl-ethyl group, 1-carboxy-2-hydroxyphenylethyl group, 4-carboxybenzyl group, etc. It may be.

In the formula (M-2b), examples of the substituted or unsubstituted alicyclic group in R ₂₁ , R ₂₂ and R ₂₃ include a cyclohexyl group and a 4-carboxycyclohexyl group.

In the formula (M-2b), examples of the substituted or unsubstituted heterocyclic group in R ₂₁ , R ₂₂ and R ₂₃ include a pyridyl group, a thiadiazolyl group, a benzothiazolyl group, 2,2,6,6-tetramethylpi And a peridinyl group. Examples of the substituent of the substituted heterocyclic group include the same substituents as the substituent of the substituted alkyl group.

In the formula (M-2b), as R ₂₁ , R ₂₂ and R ₂₃ , at least one is an alkyl group, alkenyl group, aryl group, alicyclic group substituted with 1 to 4 carboxy groups or sulfamoyl groups, or It may be a heterocyclic group.

In the formula (M-2b), R ₂₁ and R ₂₂ may each be a hydrogen atom or a trisubstituted phenyl group, and R ₂₁ and R ₂₂ may be the same or different. Here, the three substituents of the 3-substituted phenyl group are each a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 9 total carbon atoms, and a total carbon number of 1 to 9 A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonate group, and a carboxylate group, The two substituents may be the same or different.

As a preferable embodiment of the magenta dye (M-2b), for example, in the formula (M-2b), at least one of R ₂₁ , R ₂₂ and R ₂₃ is substituted with 1 to 4 carboxy groups or sulfamoyl groups. And an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a cyclohexyl group.

  The magenta dye (M-2b) preferably has a total of 6 or less, preferably 5 or less, particularly preferably 4 or less sulfonic acid groups and carboxy groups or salts thereof in the structure. The magenta dye (M-2b) may be used as it is in the free acid form, but may be used as it is when it is obtained in the salt form at the time of manufacture, or converted to the desired salt form. Also good. The magenta dye (M-2b) may have a part of the acid group in a salt form, and may contain a salt-type dye and a free acid-type dye. Examples of such salt forms include salts of alkali metals such as Na, Li, and K, ammonium salts that may be substituted with alkyl groups or hydroxyalkyl groups, and salts of organic amines. Examples of the organic amine include lower alkyl amines, hydroxy substituted lower alkyl amines, carboxy substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

As a preferable embodiment of the magenta dye (M-2b), for example, in the formula (M-2b):
r is 0;
R ₁₈ is a carboxy group, a carbamoyl group, a trifluoromethyl group or a sulfamoyl group,
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a phenyl group or a carboxyalkyl group which may be substituted with a carboxy group or a sulfamoyl group,
In one embodiment, R ₂₃ is a hydrogen atom or an alkyl group.

  Preferable specific examples of the magenta dye (M-2b) include compounds represented by formulas (M-2b-1) to (M-2b-5).

In the formula (M-2b), the compound represented by the formula (M-2b-1)
r is 0;
R ₁₈ is a carboxy group located at the 2-position of the phenyl group bonded to the azo group;
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a 2-carboxyphenyl group;
In an embodiment, R ₂₃ is a hydrogen atom. In the compound represented by the formula (M-2b-1), the sulfonic acids located at the 3rd and 6th positions of the naphthalene ring are ammonium salts.

In the formula (M-2b), the compound represented by the formula (M-2b-2)
r is 0;
R ₁₈ is a carbamoyl group located at the 2-position of the phenyl group bonded to the azo group;
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a 2-carboxyphenyl group;
In an embodiment, R ₂₃ is a hydrogen atom. In the compound represented by the formula (M-2b-2), the sulfonic acids located at the 3rd and 6th positions of the naphthalene ring are sodium salts.

In the formula (M-2b), the compound represented by the formula (M-2b-3)
r is 0;
R ₁₈ is a sulfamoyl group located at the 3-position of the phenyl group bonded to the azo group;
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a 2-sulfamoylphenyl group;
In an embodiment, R ₂₃ is an isopropyl group. In the compound represented by the formula (M-2b-3), the sulfonic acids located at the 3rd and 6th positions of the naphthalene ring are ethylammonium salts.

The compound represented by the formula (M-2b-4) is represented by the formula (M-2b):
r is 0;
R ₁₈ is a trifluoromethyl group located at the 2-position of the phenyl group bonded to the azo group,
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a 1-carboxy-2-methylbutyl group,
In an embodiment, R ₂₃ is a methyl group. In the compound represented by the formula (M-2b-4), the sulfonic acids located at the 3rd and 6th positions of the naphthalene ring are methylammonium salts.

In the formula (M-2b), the compound represented by the formula (M-2b-5)
r is 0;
R ₁₈ is a carboxy group located at the 2-position of the phenyl group bonded to the azo group;
R ₁₉ , R ₂₀ and R ₂₂ are each a hydrogen atom,
R ₂₁ is a phenyl group;
In an embodiment, R ₂₃ is a hydrogen atom. In the compound represented by the formula (M-2b-5), the sulfonic acids located at the 3rd and 6th positions of the naphthalene ring are ammonium salts.

  C. I. Acid Red 1 is a dye represented by the formula (M-2c), for example.

  The magenta dye (M-2) is the magenta dye (M-2b), C.I. I. Acid Red 1 and C.I. I. When the dye is at least one dye selected from the group consisting of Acid Red 254, light resistance and ozone resistance can be improved by including the magenta dye (M-1) in the aqueous magenta ink. The blending amount of the magenta dye (M-1) in this case is not particularly limited, but is, for example, 0.1% by weight to 10% by weight, preferably 1.4% by weight with respect to the total amount of the aqueous magenta ink. % To 5.4% by weight.

  The magenta dye (M-2) is the magenta dye (M-2b), C.I. I. Acid Red 1 and C.I. I. When the dye is at least one dye selected from the group consisting of Acid Red 254, color development can be improved by including the magenta dye (M-2) in the water-based magenta ink. The compounding amount of the magenta dye (M-2) in this case is not particularly limited, but is, for example, 0.05% by weight to 5% by weight, preferably 0.2% by weight with respect to the total amount of the aqueous magenta ink. % To 1.8% by weight.

  The magenta dye (M-2) is the magenta dye (M-2b), C.I. I. Acid Red 1 and C.I. I. In the case of at least one dye selected from the group consisting of Acid Red 254, the weight ratio of the magenta dye (M-1) to the magenta dye (M-2) in the aqueous magenta ink is magenta dye (M -1): Magenta dye (M-2) = 70: 30 to 90:10 is preferable. By setting the weight ratio in the above range, it is possible to obtain a water-based magenta ink having excellent color developability, light resistance, and ozone resistance.

  The total amount of the magenta dye (M-1) and the magenta dye (M-2) is not particularly limited, but is preferably 2% by weight to 6% by weight with respect to the total amount of the aqueous magenta ink. By setting the total blending amount within the above range, it is possible to obtain a water-based magenta ink having all of storage stability, color developability, light resistance, ozone resistance and jetting stability.

  The water-based magenta ink may further contain other magenta colorant in addition to the magenta dye (M-1) and the magenta dye (M-2). Examples of the other magenta colorant include dyes and pigments other than the magenta dye (M-1) and the magenta dye (M-2).

  The water-based magenta ink may further contain water and a water-soluble organic solvent. The water and its blending amount are the same as the water and its blending amount in the aforementioned aqueous yellow ink. The water-soluble organic solvent and the blending amount thereof are the same as the water-soluble organic solvent and the blending amount thereof in the aqueous yellow ink described above.

  The water-based magenta ink may further contain a conventionally known additive as required. The additive is the same as the additive in the aqueous yellow ink described above.

  The water-based magenta ink is prepared by, for example, uniformly mixing the magenta dye (M-1) and the magenta dye (M-2) with other additive components as necessary, using a conventionally known method, and a filter. To remove the insoluble matter.

(Water-based cyan ink)
As described above, the aqueous cyan ink contains the cyan dye (C-1).

  As described above, the cyan dye (C-1) is a dye represented by the formula (C-1).

The compound represented by the formula (C-1) may be a compound in which rings A ₃₁ , A ₃₂ and A ₃₃ are all 2,3-pyridine rings or 3,2-pyridine rings, or ring A ₃₁ , A ₃₂ and A ₃₃ may be a compound in which two of them are 2,3-pyridine rings or 3,2-pyridine rings and the other one is a benzene ring, or rings A ₃₁ , A ₃₂ and A ₃₃ One of them may be a 2,3-pyridine ring or 3,2-pyridine ring, and the remaining two may be a benzene ring.
The cyan dye (C-1) may be composed of a single compound or a mixture containing two or more compounds.

  Preferable specific examples of the cyan dye (C-1) include compounds represented by the formulas (C-1a) to (C-1f).

式（Ｃ−１ａ）において、
環Ａ_３１、Ａ_３２及びＡ_３３は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、
ａは、１．０であり、ｂは、１．８であり、ｃは、１．２であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1a),
Rings A ₃₁ , A ₃₂ and A ₃₃ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring,
a is 1.0, b is 1.8, c is 1.2, and a, b and c are average values in the mixture.

式（Ｃ−１ｂ）において、
環Ａ_３１及びＡ_３２は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、環Ａ_３３は、ベンゼン環であり、
ａは、２．４であり、ｂは、０．６であり、ｃは、１．０であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1b),
Ring A ₃₁ and A ₃₂ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring, Ring A ₃₃ is a benzene ring,
a is 2.4, b is 0.6, c is 1.0, and a, b and c are average values in the mixture.

式（Ｃ−１ｃ）において、
環Ａ_３１、Ａ_３２及びＡ_３３は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、
ａは、３．０であり、ｂは、０．２であり、ｃは、０．８であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1c),
Rings A ₃₁ , A ₃₂ and A ₃₃ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring,
a is 3.0, b is 0.2, c is 0.8, and a, b and c are average values in the mixture.

式（Ｃ−１ｄ）において、
環Ａ_３１は、ベンゼン環であり、環Ａ_３２及びＡ_３３は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、
ａは、１．８であり、ｂは、０．９であり、ｃは、１．３であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1d),
Ring A ₃₁ is a benzene ring, and Rings A ₃₂ and A ₃₃ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring,
a is 1.8, b is 0.9, c is 1.3, and a, b and c are average values in the mixture.

式（Ｃ−１ｅ）において、
環Ａ_３１、Ａ_３２及びＡ_３３は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、
ａは、１．１であり、ｂは、１．３であり、ｃは、１．６であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1e),
Rings A ₃₁ , A ₃₂ and A ₃₃ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring,
a is 1.1, b is 1.3, c is 1.6, and a, b and c are average values in the mixture.

式（Ｃ−１ｆ）において、
環Ａ_３１及びＡ_３３は、それぞれ独立に、２，３−ピリジン環及び／又は３，２−ピリジン環であり、環Ａ_３２は、ベンゼン環であり、
ａは、０であり、ｂは、１．８であり、ｃは、２．２であり、ａ、ｂ及びｃは、混合物における平均値である。

In the formula (C-1f),
Ring A ₃₁ and A ₃₃ are each independently a 2,3-pyridine ring and / or a 3,2-pyridine ring, Ring A ₃₂ is a benzene ring,
a is 0, b is 1.8, c is 2.2, and a, b and c are average values in the mixture.

式（Ｃ−２ａ）において、
Ｐｃ（Ｃｕ）は、式（Ｐｃ）で表される銅フタロシアニン核であり、
Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４は、それぞれ、−ＳＯ_２Ｒ_ａ、−ＳＯ_２ＮＲ_ｂＲ_ｃ及び−ＣＯ_２Ｒ_ａからなる群から選択される置換基であり、Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４のすべてが同一であることはなく、Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４の少なくとも一つは、イオン性親水性基を置換基として有し、Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４の少なくとも一つは、式（Ｐｃ）で表される銅フタロシアニン核中の４つのベンゼン環Ａ、Ｂ、Ｃ及びＤのそれぞれに存在し、Ｒ_ａは、置換又は無置換のアルキル基であり、Ｒ_ｂは、水素原子、置換又は無置換のアルキル基であり、Ｒ_ｃは、置換又は無置換のアルキル基であり、
ｋは、０＜ｋ＜８を満たし、ｌは、０＜ｌ＜８を満たし、ｍは、０≦ｍ＜８を満たし、ｎは、０≦ｎ＜８を満たし、かつ、ｋ、ｌ、ｍ及びｎは、４≦ｋ＋ｌ＋ｍ＋ｎ≦８を満たす。

式（Ｃ−２ｂ）において、
Ｐｃ（Ｃｕ）は、式（Ｐｃ）で表される銅フタロシアニン核であり、
Ｍ_０は、リチウム、ナトリウム、カリウム及びＮＨ_４のいずれかであり、
ｘは、０＜ｘ＜４を満たし、ｙは、０＜ｙ＜４を満たし、かつ、ｘ及びｙは、２≦ｘ＋ｙ≦５を満たし、
ＳＯ_３Ｍ_０基及びＳＯ_２ＮＨ_２基は、式（Ｐｃ）で表される銅フタロシアニン核中の４つのベンゼン環Ａ、Ｂ、Ｃ及びＤのいずれかに存在する。

In addition to the cyan dye (C-1), the water-based cyan ink may further contain other cyan colorants such as dyes and pigments other than the cyan dye (C-1). Examples of the other cyan colorant include the following cyan dye (C-2).

Cyan dye (C-2): a dye represented by the formula (C-2a), a dye represented by the formula (C-2b), C.I. I. Direct Blue 199 and C.I. I. At least one dye selected from the group consisting of Direct Blue 86

In formula (C-2a),
Pc (Cu) is a copper phthalocyanine nucleus represented by the formula (Pc),
R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a substituent selected from the group consisting of —SO ₂ R _a , —SO ₂ NR _b R _c and —CO ₂ R _a , and R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are not all the same, and at least one of R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ has an ionic hydrophilic group as a substituent, and R ₃₁ , R _32, at least one of _{R 33} and _{R 34} are present four benzene rings a of the copper phthalocyanine nucleus represented by the formula (Pc), B, respectively C and D, _{R a} is a substituted or unsubstituted A substituted alkyl group, R _b is a hydrogen atom, a substituted or unsubstituted alkyl group, R _c is a substituted or unsubstituted alkyl group,
k satisfies 0 <k <8, l satisfies 0 <l <8, m satisfies 0 ≦ m <8, n satisfies 0 ≦ n <8, and k, l, m and n satisfy 4 ≦ k + 1 + m + n ≦ 8.

In formula (C-2b),
Pc (Cu) is a copper phthalocyanine nucleus represented by the formula (Pc),
M ₀ is any one of lithium, sodium, potassium and NH ₄ ,
x satisfies 0 <x <4, y satisfies 0 <y <4, and x and y satisfy 2 ≦ x + y ≦ 5,
The SO ₃ M ₀ group and the SO ₂ NH ₂ group are present in any of the four benzene rings A, B, C, and D in the copper phthalocyanine nucleus represented by the formula (Pc).

  In the formula (C-2a), the substituted or unsubstituted alkyl group is preferably a linear, branched or alicyclic alkyl group having 1 to 12 carbon atoms. From the viewpoint of improving the solubility of the dye and the stability of the aqueous cyan ink, the alkyl group preferably has a branched chain, and particularly preferably has an asymmetric carbon (use in racemic form). Examples of the substituted or unsubstituted alkyl group include a methyl group, ethyl group, n-butyl group, isopropyl group, tert-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3- Examples thereof include a sulfopropyl group and a 4-sulfobutyl group.

  In the formula (C-2a), examples of the substituent of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, 2 A linear or branched alkyl group having 1 to 12 carbon atoms such as a methylsulfonylethyl group, a 3-phenoxypropyl group, a trifluoromethyl group, or a cyclopentyl group; a linear or branched aralkyl group having 7 to 18 carbon atoms; A linear or branched alkenyl group having 2 to 12 carbon atoms; a linear or branched alkynyl group having 2 to 12 carbon atoms; a linear or branched cycloalkyl group having 3 to 12 carbon atoms; 3-12 linear or branched cycloalkenyl groups; halogen atoms such as chlorine atom and bromine atom; phenyl group, 4-tert-butylphenyl group, 2,4-di-te aryl groups such as t-aminophenyl group; heterocyclic groups such as imidazolyl group, pyrazolyl group, triazolyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group; cyano group; hydroxyl group; Nitro group; carboxy group; amino group; alkoxy group such as methoxy group, ethoxy group, 2-methoxyethoxy group, 2-methanesulfonylethoxy group; phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3 -Aryloxy groups such as nitrophenoxy group, 3-tert-butoxycarbamoylphenoxy group, 3-methoxycarbamoyl group; acylamino groups such as acetamide group, benzamide group, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide group Group: methylamino group, butylamino Group, alkylamino group such as diethylamino group and methylbutylamino group; anilino group such as phenylamino group and 2-chloroanilino group; ureido group such as phenylureido group, methylureido group and N, N-dibutylureido group; Sulfamoylamino groups such as N-dipropylsulfamoylamino group; alkylthio groups such as methylthio group, octylthio group and 2-phenoxyethylthio group; phenylthio group, 2-butoxy-5-tert-octylphenylthio group, 2 -Arylthio group such as carboxyphenylthio group; alkoxycarbonylamino group such as methoxycarbonylamino group; sulfonamide group such as methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group; N-ethylcarbamoyl group, N , N-Dipropylsulfur A sulfamoyl group such as a famoyl group and an N-phenylsulfamoyl group; a sulfonyl group such as a methanesulfonyl group, an octanesulfonyl group, a benzenesulfonyl group and a toluenesulfonyl group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; Heterocyclic oxy groups such as phenyltetrazol-5-oxy group and 2-tetrahydroxypyranyloxy group; phenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propa Azo groups such as noylphenylazo group; acyloxy groups such as acetoxy group; carbamoyloxy groups such as N-methylcarbamoyloxy group and N-phenylcarbamoyloxy group; silyloxy groups such as trimethylsilyloxy group and dibutylmethylsilyloxy group Aryloxycarbonylamino groups such as phenoxycarbonylamino group; imide groups such as N-succinimide group and N-phthalimide group; 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6 Heterocyclic thio groups such as thio groups and 2-pyridylthio groups; sulfinyl groups such as 3-phenoxypropylsulfinyl groups; phosphonyl groups such as phenoxyphosphonyl groups, octyloxyphosphonyl groups and phenylphosphonyl groups; Aryloxycarbonyl group; acyl group such as acetyl group, 3-phenylpropanoyl group and benzoyl group; ionic hydrophilic group such as carboxy group, sulfo group, phosphono group and quaternary ammonium group. The alkyl group, the aralkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, and the cycloalkenyl group, which are substituents of the substituted alkyl group, improve dye solubility and aqueous cyan ink stability. From the viewpoint, those having a branched chain are preferred, and those having an asymmetric carbon are particularly preferred.

As a preferable aspect of the cyan dye (C-2a), for example, in the formula (C-2a), R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each —SO ₂ R _a , R ₃₁ , all R _32, R ₃₃ and R ₃₄ is R _a having each not be the same, at least one of R _a is an embodiment which is a substituted alkyl group having an ionic hydrophilic group.

  As a more preferred embodiment of the cyan dye (C-2a), for example, in the formula (C-2a), k satisfies 0 <k <4, l satisfies 0 <l <4, and m is In this embodiment, 0 ≦ m <4 is satisfied, n satisfies 0 ≦ n <4, and k, l, m, and n satisfy k + l + m + n = 4.

  Preferable specific examples of the cyan dye (C-2a) include compounds represented by formulas (C-2a-1) to (C-2a-5).

In the compound represented by the formula (C-2a-1), in the formula (C-2a), R ₃₁ is a lithium sulfonatopropylsulfonyl group, and R ₃₂ is an N- (2-hydroxypropyl) sulfamoylpropylsulfonyl group. In which k is 3, l is 1, m and n are both 0.

In the compound represented by the formula (C-2a-2), in the formula (C-2a), R ₃₁ is a lithium sulfonatopropylsulfonyl group, and R ₃₂ is an N- (2-hydroxyisopropyl) sulfamoylpropylsulfonyl group. In which k is 3, l is 1, m and n are both 0.

In the compound represented by the formula (C-2a-3), in the formula (C-2a), R ₃₁ is a lithium sulfonatopropylsulfonyl group, and R ₃₂ is N, N- (di (2-hydroxyethyl)) sulfur. In this embodiment, it is a famoylpropylsulfonyl group, k is 3, 1 is 1, m and n are both 0.

In the compound represented by the formula (C-2a-4), in the formula (C-2a), R ₃₁ is a lithium sulfonatopropylsulfonyl group, and R ₃₂ is an N- (2-hydroxypropyl) sulfamoylpropylsulfonyl group. , R ₃₃ is an N- (2-hydroxyisopropyl) sulfamoylpropylsulfonyl group, k is 2, 1 is 1, m is 1, and n is 0.

In the compound represented by the formula (C-2a-5), in the formula (C-2a), R ₃₁ is a lithium sulfonatopropylsulfonyl group, R ₃₂ is a lithium carboxylatopropylsulfonyl group, and R ₃₃ is N- (2 -Hydroxypropyl) sulfamoylpropylsulfonyl group, R ₃₄ is an N- (2-hydroxyisopropyl) sulfamoylpropylsulfonyl group, and k, l, m, and n are all 1.

In the formula (C-2b), the M ₀ may be ionized (any one of Li ⁺ , Na ⁺ , K ⁺ and NH ₄ ⁺ ) by ionization in an aqueous cyan ink.
In the water-based cyan ink, in the formula (C-2b), x and y may satisfy x + y = 4.

  Preferable specific examples of the cyan dye (C-2b) include compounds represented by formulas (C-2b-1) to (C-2b-4).

The compound represented by the formula (C-2b-1) is a copper phthalocyanine represented by the formula (Pc) in which M ₀ is sodium, x is 1 and y is 3 in the formula (C-2b). In this embodiment, one substituent is present in each of the four benzene rings A, B, C and D in the nucleus.

The compound represented by the formula (C-2b-2) is a copper phthalocyanine represented by the formula (Pc) in which M ₀ is sodium, x is 2 and y is 2 in the formula (C-2b). In this embodiment, one substituent is present in each of the four benzene rings A, B, C and D in the nucleus.

The compound represented by the formula (C-2b-3) is a copper phthalocyanine represented by the formula (Pc) in which M ₀ is sodium, x is 3 and y is 1 in the formula (C-2b). In this embodiment, one substituent is present in each of the four benzene rings A, B, C and D in the nucleus.

The compound represented by the formula (C-2b-4) is a copper phthalocyanine represented by the formula (Pc) in which M ₀ is ammonium, x is 1 and y is 3 in the formula (C-2b) In this embodiment, one substituent is present in each of the four benzene rings A, B, C and D in the nucleus.

  C. I. Direct blue 199 is, for example, a dye represented by the formula (C-2c).

  C. I. The direct blue 86 is, for example, a dye represented by the formula (C-2d).

  In the case of using the cyan dye (C-2) in addition to the cyan dye (C-1), the blending amount of the cyan dye (C-1) is not particularly limited. If the cyan dye (C-1) is contained in the aqueous cyan ink, the storage stability, light resistance, ozone resistance and jetting stability can be improved. The blending amount of the cyan dye (C-1) is, for example, 0.1 wt% to 10 wt%, preferably 1.4 wt% to 5.7 wt% with respect to the total amount of the aqueous cyan ink. Yes, more preferably from 1.6% to 4.8% by weight.

  In the case of using the cyan dye (C-2) in addition to the cyan dye (C-1), the amount of the cyan dye (C-2) is not particularly limited. If the cyan dye (C-2) is included in the aqueous cyan ink, the color developability can be improved. The blending amount of the cyan dye (C-2) is, for example, 0.05 wt% to 5 wt%, preferably 0.1 wt% to 1.8 wt%, with respect to the total amount of the aqueous cyan ink. Yes, more preferably from 0.1 wt% to 1.5 wt%.

  When the cyan dye (C-2) is used in addition to the cyan dye (C-1), the weight ratio of the cyan dye (C-1) to the cyan dye (C-2) in the aqueous cyan ink is Cyan dye (C-1): Cyan dye (C-2) = 70: 30 to 95: 5 is preferable. By setting the weight ratio within the above range, it is possible to obtain a water-based cyan ink having very good ejection stability in addition to storage stability, color development, light resistance, and ozone resistance.

  The total amount of the cyan dye (C-1) and the cyan dye (C-2) is not particularly limited, but is preferably 2% by weight to 7% by weight with respect to the total amount of the aqueous cyan ink. By setting the total blending amount within the above range, it is possible to obtain an aqueous cyan ink having extremely good storage stability, color developability, light resistance, ozone resistance and jetting stability.

  The water-based cyan ink may further contain water and a water-soluble organic solvent. The water and its blending amount are the same as the water and its blending amount in the aforementioned aqueous yellow ink. The water-soluble organic solvent and the blending amount thereof are the same as the water-soluble organic solvent and the blending amount thereof in the aqueous yellow ink described above.

  The water-based cyan ink may further contain a conventionally known additive as required. The additive is the same as the additive in the aqueous yellow ink described above.

  The water-based cyan ink is obtained by, for example, uniformly mixing the cyan dye (C-1) and other additive components as necessary by a conventionally known method, and removing insoluble matters with a filter or the like. Can be prepared.

  The ink jet recording apparatus and the ink jet recording method of the present invention can support full color recording by using the three color aqueous inks. In the ink jet recording apparatus and the ink jet recording method of the present invention, only the three color water-based inks may be used, or other color water-based inks may be used. Examples of the other color water-based inks include water-based black ink, water-based red ink, water-based green ink, water-based blue ink, and water-based light ink having a low colorant concentration (water-based light yellow ink, water-based light magenta ink, water-based light cyan ink). Water-based light black ink, water-based light red ink, water-based light green ink, water-based light blue ink, etc.). In the ink jet recording apparatus and the ink jet recording method of the present invention, it is preferable to use water-based black ink because it is possible to cope with full color recording.

  Next, the ink jet recording apparatus of the present invention includes an ink containing portion, an ink discharge means, and a control means. The ink storage unit can store the water yellow ink, water magenta ink, and water cyan ink. In the ink jet recording apparatus of the present invention, the configuration other than the control means can be the same as that of the conventional ink jet recording apparatus.

  FIG. 2 shows an example of the configuration of the ink jet recording apparatus of the present invention (excluding control means). As shown in the figure, this ink jet recording apparatus 1 includes four ink cartridges 2, an ink discharge means (ink jet head) 3, a head unit 4, a carriage 5, a drive unit 6, a platen roller 7, and a purge device 8. Are included as main components.

  The four ink cartridges 2 contain one color each of four colors of water-based inks of yellow, magenta, cyan, and black. The ink jet head 3 installed in the head unit 4 performs recording on a recording medium (for example, recording paper) P. Four ink cartridges 2 and a head unit 4 are mounted on the carriage 5. The drive unit 6 reciprocates the carriage 5 in the linear direction. As the drive unit 6, for example, a conventionally known one can be used (for example, see Japanese Patent Laid-Open No. 2008-246821). The platen roller 7 extends in the reciprocating direction of the carriage 5 and is disposed to face the inkjet head 3.

  The purge device 8 sucks out defective ink containing bubbles and the like accumulated in the ink jet head 3. As the purge device 8, for example, a conventionally known device can be used (see, for example, JP-A-2008-246821).

  A wiper member 20 is disposed adjacent to the purge device 8 on the platen roller 7 side of the purge device 8. The wiper member 20 is formed in a spatula shape, and wipes the nozzle formation surface of the inkjet head 3 as the carriage 5 moves. In FIG. 2, a cap 18 covers a plurality of nozzles of the inkjet head 3 that is returned to the reset position when recording is completed in order to prevent the water-based ink from drying.

  In the ink jet recording apparatus 1 of this example, four ink cartridges 2 are mounted on one carriage 5 together with the head unit 4. However, the present invention is not limited to this. In the ink jet recording apparatus, each of the four ink cartridges 2 may be mounted on a carriage different from the head unit 4. Further, each of the four ink cartridges 2 may not be mounted on the carriage 5 but may be arranged and fixed in the ink jet recording apparatus. In these aspects, for example, each cartridge of the four ink cartridges 2 and the head unit 4 mounted on the carriage 5 are connected by a tube or the like, and each cartridge of the four ink cartridges 2 is connected to the head unit 4 from the cartridge. Aqueous ink is supplied.

  Ink jet recording using this ink jet recording apparatus 1 is performed as follows, for example. First, the recording paper P is fed from a paper feed cassette (not shown) provided on the side of or below the ink jet recording apparatus 1. The recording paper P is introduced between the inkjet head 3 and the platen roller 7. Predetermined recording is performed on the introduced recording paper P by water-based ink ejected from the inkjet head 3. The recording sheet P after recording is discharged from the inkjet recording apparatus 1. In FIG. 2, the paper feed mechanism and paper discharge mechanism for the recording paper P are not shown.

  The ink jet recording apparatus of the present invention may be the serial type ink jet recording apparatus shown in FIG. 2 or a line type ink jet recording apparatus.

Next, in the ink jet recording apparatus and the ink jet recording method of the present invention, the water-based yellow ink, water-based magenta ink, and water-based cyan ink are used to form a composite on glossy paper so as to satisfy the following conditions (A) and (B). Form black.

(A) 0.68 ≦ M / (Y + C)
(B) 500 ≦ Y + M + C ≦ 600
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the yellow dye (Y-1) and the yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the magenta dye (M-1) and the magenta dye (M-2)
C: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the cyan dye (C-1)

  The magenta dye (M-1) is likely to change in the ease of diffusion to the recording medium in a high humidity environment. For this reason, when the aqueous magenta ink is mixed with the aqueous yellow ink and aqueous cyan ink on a recording medium to record composite black, the magenta dye (M-1) diffuses in the high humidity environment. The color tone of magenta in the composite black becomes weak, and an achromatic color (for example, a color in a gradation range from black (black) to gray (gray)) may appear greenish. On the other hand, in the ink jet recording apparatus and the ink jet recording method of the present invention, the magenta dye tends to remain on the glossy paper by increasing the ratio of the magenta dye in the composite black so as to satisfy the condition (A). Therefore, it is possible to suppress a phenomenon that looks green in a high humidity environment. However, simply increasing the ratio of the magenta dye may cause the composite black to appear reddish under normal humidity conditions. On the other hand, in the ink jet recording apparatus and the ink jet recording method of the present invention, by controlling the total amount of the three primary color dyes within a predetermined range so as to satisfy the condition (B), in a normal humidity environment, While suppressing the phenomenon that the composite black appears reddish, it is possible to suppress the phenomenon that appears greenish in a high humidity environment.

  Next, the formation of the composite black in the ink jet recording apparatus and the ink jet recording method of the present invention will be described with an example.

  FIG. 1 shows a flowchart (FIG. 1A) and a block diagram (FIG. 1B) of an example of the composite black formation. The block diagram of FIG. 1B shows the relationship among the ink cartridge (ink storage unit) 2, the inkjet head (ink ejection unit) 3, and the control unit 11 in the inkjet recording apparatus 1 of the present invention. In this example, the control means 11 includes a central processing unit (CPU) 11a, a ROM (Read Only Memory) 11b, and a RAM (Random Access Memory) 11c. However, the control means 11 is not limited to this example. The inkjet head 3 has a nozzle row composed of a plurality of nozzles for each color, and the nozzle rows are arranged in order of water-based black ink, water-based yellow ink, water-based cyan ink, and water-based magenta ink in the scanning direction. Yes. This arrangement order is merely an example, and may be arranged in a different order.

  The composite black is formed in the ink jet recording apparatus and the ink jet recording method of this example, for example, as follows. In this example, solid black printing is performed.

First, as shown in FIGS. 1A and 1B, when the recording operation is started, the carriage on which the ink cartridge 2 is mounted starts to move in the scanning direction, and the control means 11 reaches the position where the composite black is formed. It is determined whether it has been (S1). If it is determined that the composite black formation position has not been reached (No), the color portion other than the composite black is formed. The formation of the color portion may include formation of a black portion using a monochromatic aqueous black ink. If it is determined that the composite black formation position has been reached (Yes), droplets are ejected from the inkjet head 3 in the order of the aqueous yellow ink, the aqueous cyan ink, and the aqueous magenta ink at a predetermined print duty. Discharge. This print duty corresponds to a value set so as to satisfy the conditions (A) and (B). The “duty” is defined as follows. There is no restriction on the order of execution and the number of executions of the color portion formation and the composite black formation, and can be appropriately changed according to a desired image. By controlling the specific yellow dye, magenta dye and cyan dye dripped onto the predetermined area of the glossy paper so as to satisfy the conditions (A) and (B), the color change of the composite black can be suppressed, and Excellent fixability.

duty (%) = number of actual recording dots / (vertical resolution × horizontal resolution) × 100
Actual recording dot number: Actual recording dot number per unit area Vertical resolution: Vertical resolution per unit area Horizontal resolution: Horizontal resolution per unit area

In the ink jet recording apparatus and the ink jet recording method of the present invention, it is preferable that the control means 11 controls the ink jet head 3 to satisfy the following condition (A2) to form composite black on glossy paper. By satisfying the following condition (A2), the color change of the composite black under a high humidity environment can be further suppressed.

(A2) 0.75 ≦ M / (Y + C)
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the yellow dye (Y-1) and the yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the magenta dye (M-1) and the magenta dye (M-2)
C: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the cyan dye (C-1)

  In the ink jet recording apparatus and the ink jet recording method of the present invention, the glossy paper is preferably glossy paper having a void type resin coat layer. By using such glossy paper, the color change of the composite black can be further suppressed and the fixability is also excellent.

  Next, the recorded matter of the present invention is recorded by the ink jet recording method of the present invention. The recorded matter of the present invention recorded by the ink jet recording method of the present invention can suppress the color change of the composite black and has excellent fixability.

  Next, the composite black of the present invention is recorded on glossy paper using the water-based yellow ink, water-based magenta ink, and water-based cyan ink so as to satisfy the conditions (A) and (B). And The composite black of the present invention can suppress color change and is excellent in fixability. In the composite black of the present invention, conditions such as the composition of the water-based yellow ink, water-based magenta ink, and water-based cyan ink may be the same as those in the ink jet recording method of the present invention described above.

  Next, examples of the present invention will be described together with comparative examples. In addition, this invention is not limited and restrict | limited by the following Example and comparative example.

[Preparation of water-based yellow ink]
The ink composition components (Table 2) were mixed uniformly. Thereafter, the obtained mixture was filtered using a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size 0.20 μm) manufactured by Toyo Roshi Kaisha, Ltd., thereby obtaining aqueous yellow inks Y1 to Y6. . In Table 2, yellow dyes (Y-1a) to (Y-1e) are compounds represented by formulas (Y-1a) to (Y-1e), respectively.

[Preparation of water-based magenta ink]
The ink composition components (Table 3) were mixed uniformly. Thereafter, the obtained mixture was filtered using a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size 0.20 μm) manufactured by Toyo Roshi Kaisha, Ltd., thereby obtaining aqueous magenta inks M1 to M7. . In Table 3, magenta dyes (M-1a) to (M-1d) are compounds represented by magenta dyes (M-1a) to (M-1d) shown in Table 1, respectively. (M-2a-2) to (M-2a-4) are compounds represented by formulas (M-2a-2) to (M-2a-4), respectively, and a magenta dye (M-2b-). 2) is a compound represented by the formula (M-2b-2).

[Preparation of water-based cyan ink]
The ink composition components (Table 4) were mixed uniformly. Thereafter, the obtained mixture was filtered using a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size 0.20 μm) manufactured by Toyo Roshi Kaisha, Ltd., thereby obtaining aqueous cyan inks C1 to C7. . In Table 4, cyan dyes (C-1a) to (C-1d) are compounds represented by formulas (C-1a) to (C-1d), respectively, and cyan dyes (C-2a- 1), (C-2a-2) and (C-2a-5) are respectively represented by formulas (C-2a-1), (C-2a-2) and (C-2a-5). A compound.

[Examples 1-14 and Comparative Examples 1-15]
Photographic glossy paper manufactured by Brother Industries, Ltd. using a water-based yellow ink, water-based magenta ink, and water-based cyan ink shown in Table 5 using a digital multifunction printer DCP-J525N equipped with an inkjet printer manufactured by Brother Industries, Ltd. Composite black is formed on BP71G, (a) color evaluation (normal temperature and humidity), (b) color evaluation (low temperature and high humidity), (c) light resistance evaluation, (d) fixability evaluation, and (e) Comprehensive evaluation was performed by the following method.

(A) Color evaluation (room temperature and humidity)
The composite black was formed in an environment at a temperature of 25 ° C. and a relative humidity of 50%, and was stored for 24 hours in the same environment as that at the time of formation to obtain a room temperature and normal humidity environment sample. The a * value of the ambient temperature and humidity environment sample was measured by a spectrocolorimeter SpectroEye manufactured by Gretag Macbeth (measurement field of view: 2 °; white standard: Abs (absolute white); light source: D ₅₀ ; concentration standard: ANSI T). Measured and evaluated according to the following evaluation criteria.

Color evaluation (normal temperature and humidity) Evaluation standard AA: | a * | value (absolute value of a * value) is less than 2.0 A: | a * | value is 2.0 or more and less than 3.0 B: | A * | The value is 3.0 or more

(B) Color evaluation (low temperature and high humidity)
The composite black was formed in an environment at a temperature of 18 ° C. and a relative humidity of 80%, and was stored for 24 hours in the same environment as in the formation to obtain a low temperature and high humidity environment sample. The a * value of the low-temperature and high-humidity environment sample was measured in the same manner as in the (a) color evaluation (normal temperature and normal humidity), and evaluated according to the following evaluation criteria.

Color evaluation (low temperature and high humidity) Evaluation standard AA: a * value is −8.5 or more A: a * value is −9.5 or more and less than −8.5 B: a * value is −9.5 Less than

(C) Light fastness evaluation Using the water-based magenta ink shown in Table 5 using the above-mentioned digital multifunction device DCP-J525N equipped with an inkjet printer, the water-based magenta ink was placed on photographic glossy paper BP71G manufactured by Brother Industries, Ltd. A gradation patch was recorded. Among the gradation patches, a patch having an initial OD value of 1.0 was used as an evaluation sample. The OD value was measured by a spectrocolorimeter Spectrolino (measuring field of view: 2 °; white standard: Abs (absolute white); light source: D ₆₅ ; density standard: ANSI A) manufactured by Gretag Macbeth. Using the Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd., the evaluation sample was irradiated with xenon lamp light for 100 hours under the conditions of a bath temperature of 23 ° C., a bath relative humidity of 50%, and an illuminance of 81 klx. Subsequently, the OD value of the evaluation sample after the irradiation was measured in the same manner as described above. Next, the OD value reduction rate (%) was obtained by the following formula (I), and the light resistance was evaluated according to the following evaluation criteria. Note that the smaller the OD value reduction rate, the less the image quality is deteriorated and the better the light resistance.

OD value decrease rate (%) = {(XY) / X} × 100 (I)
X: 1.0 (initial OD value)
Y: OD value after irradiation

Light resistance evaluation Evaluation standard AA: OD value reduction rate is less than 20% A: OD value reduction rate is 20% or more and less than 30% B: OD value reduction rate is 30% or more and less than 40% C: OD value reduction rate But over 40%

(D) Fixability evaluation The composite black was formed in an environment at a temperature of 25 ° C. and a relative humidity of 50%. After 5 seconds from the formation, the composite black forming portion was rubbed with a cotton swab and the bleeding of the forming portion was visually observed. And evaluated according to the following evaluation criteria.

Fixability evaluation Evaluation criteria A: Almost no ink flow from the forming part B: Ink flow from the forming part was seen

(E) Comprehensive evaluation Comprehensive evaluation was performed according to the following evaluation criteria from the results of (a) to (d).

Comprehensive evaluation Evaluation criteria G: B and C were absent in any of the evaluation results.
NG: B or C was found in any of the evaluation results.

  Table 5 shows the structures and evaluation results of the water-based yellow ink, water-based magenta ink, and water-based cyan ink used in Examples and Comparative Examples.

  As shown in Table 5, in Examples 1 to 14, all the results of the color evaluation (normal temperature and normal humidity), the color evaluation (low temperature and high humidity), the light resistance evaluation and the fixability evaluation were good. In Examples 1 to 6, 13, and 14, which satisfy the condition (A2) and have a higher ratio of magenta dye in composite black, the results of the color evaluation (low temperature and high humidity) were particularly good.

  On the other hand, in Comparative Examples 1 to 3 where 0.68> M / (Y + C) and the ratio of the magenta dye in the composite black was low, the result of the color evaluation (low temperature and high humidity) was poor, and the yellow dye and the cyan dye The balance was lost, and the results of color evaluation (room temperature and humidity) were also poor. In Comparative Examples 4 to 11 where 500> Y + M + C and the ratio of the magenta dye in the three primary color dyes is high, the result of the color evaluation (normal temperature and humidity) was poor. In Comparative Examples 12 and 13 where Y + M + C> 600 and the total amount of the dye on the glossy paper was large, the result of the fixability evaluation was bad. Further, the magenta dye is C.I. I, Acid Red 1 or C.I. I. In Comparative Examples 14 and 15 using the aqueous magenta ink that is Acid Red 254, the results of the light resistance evaluation were poor.

  As described above, according to the present invention, it is possible to form a composite black that can suppress color change and has excellent fixability. The formation of the composite black of the present invention can be widely applied to various ink jet recordings.

DESCRIPTION OF SYMBOLS 1 Inkjet recording device 2 Ink accommodating part (ink cartridge)
3 Ink ejection means (inkjet head)
4 Head unit 5 Carriage 6 Drive unit 7 Platen roller 8 Purge device 11 Control means

Claims (10)

Including an ink container and an ink discharge means,
An ink jet recording apparatus capable of storing the following aqueous yellow ink, aqueous magenta ink, and aqueous cyan ink in the ink storage unit,
And further includes a control means,
The ink jet recording apparatus, wherein the control means controls the ink discharge means so as to satisfy the following conditions (A) and (B) to form composite black on glossy paper.

(A) 0.68 ≦ M / (Y + C)
(B) 500 ≦ Y + M + C ≦ 600
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following yellow dye (Y-1) and yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following magenta dye (M-1) and magenta dye (M-2)
C: Drip amount (ng) per glossy paper 25.4 mm × 25.4 mm of the following cyan dye (C-1)

Water-based yellow ink: Water-based ink containing the following yellow dye (Y-1) and yellow dye (Y-2) Water-based magenta ink: Water-based ink aqueous cyan containing the following magenta dye (M-1) and magenta dye (M-2) Ink: Water-based ink containing the following cyan dye (C-1)

Yellow dye (Y-1): Dye represented by formula (Y-1) Yellow dye (Y-2): C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132 and C.I. I. At least one dye selected from the group consisting of Direct Yellow 142

Magenta dye (M-1): Dye represented by formula (M-1) Magenta dye (M-2): Dye represented by formula (M-2a), Dye represented by formula (M-2b) , C.I. I. Acid Red 1 and C.I. I. At least one dye selected from the group consisting of Acid Red 254

Cyan dye (C-1): Dye represented by formula (C-1)

In the formula (Y-1),
R ₁ , R ₂ , Y ₁ and Y ₂ are each a monovalent group, and R ₁ , R ₂ , Y ₁ and Y ₂ may be the same or different,
X ₁ and X ₂ are each an electron-withdrawing group, and X ₁ and X ₂ may be the same or different,
Z ₁ and Z ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, A cyclic group, Z ₁ and Z ₂ may be the same or different;
M ₁ is a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group).

In the formula (M-1),
n ₁ is 1 or 2,
The three M's are each sodium or NH ₄ , and the three M's may be the same or different;
R ₀ is a monoalkylamino group having 1 to 8 carbon atoms substituted with a carboxy group.

In the formula (M-2a),
R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
R ₁₂ is a hydrogen atom, a halogen atom or a cyano group,
R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted sulfonyl group. A substituted or unsubstituted acyl group, and R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different, but R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ is not both a hydrogen atom,
A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one is a substituted or unsubstituted carbon atom and the other is a carbon atom.

In formula (M-2b),
r is 0, 1 or 2;
R ₁₈ , R ₁₉ and R ₂₀ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. A sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a carboxy group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, substituted or unsubstituted It is an unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.

In formula (C-1),
Rings A ₃₁ , A ₃₂ and A ₃₃ are at least one selected from the group consisting of a benzene ring, a 2,3-pyridine ring and a 3,2-pyridine ring, respectively, and the rings A ₃₁ , A ₃₂ And at least one of A ₃₃ is a 2,3-pyridine ring or a 3,2-pyridine ring, and the rings A ₃₁ , A ₃₂ and A ₃₃ may be the same or different,
a satisfies 0 ≦ a ≦ 4, b satisfies 0 ≦ b ≦ 4, c satisfies 0 ≦ c ≦ 4, and a, b, and c satisfy 0 ≦ a + b + c ≦ 4,
z is an integer satisfying 1 ≦ z ≦ 3,
R ₃₀ is a linear alkylene group having 1 to 6 carbon atoms. 2. The ink jet recording apparatus according to claim 1, wherein the control unit controls the ink discharge unit so as to satisfy the following condition (A2) to form composite black on glossy paper.

(A2) 0.75 ≦ M / (Y + C)
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the yellow dye (Y-1) and the yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the magenta dye (M-1) and the magenta dye (M-2)
C: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the cyan dye (C-1)
The total amount of the yellow dye (Y-1) and the yellow dye (Y-2) is 2% by weight to 6% by weight with respect to the total amount of the water-based yellow ink,
The total amount of the magenta dye (M-1) and the magenta dye (M-2) is 2% by weight to 6% by weight with respect to the total amount of the water-based magenta ink.
3. The ink jet recording apparatus according to claim 1, wherein the amount of the cyan dye (C-1) is 2% by weight to 7% by weight with respect to the total amount of the aqueous cyan ink. The inkjet recording apparatus according to any one of claims 1 to 3, wherein the glossy paper is glossy paper having a void type resin coat layer. An inkjet recording method for recording using the following aqueous yellow ink, aqueous magenta ink, and aqueous cyan ink,
An inkjet recording method comprising a composite black forming step of forming composite black on glossy paper so as to satisfy the following conditions (A) and (B):

(A) 0.68 ≦ M / (Y + C)
(B) 500 ≦ Y + M + C ≦ 600
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following yellow dye (Y-1) and yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following magenta dye (M-1) and magenta dye (M-2)
C: Drip amount (ng) per glossy paper 25.4 mm × 25.4 mm of the following cyan dye (C-1)

Water-based yellow ink: Water-based ink containing the following yellow dye (Y-1) and yellow dye (Y-2)

Water-based magenta ink: Water-based ink containing the following magenta dye (M-1) and magenta dye (M-2)

Water-based cyan ink: Water-based ink containing the following cyan dye (C-1)

Yellow dye (Y-1): Dye represented by formula (Y-1) Yellow dye (Y-2): C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132 and C.I. I. At least one dye selected from the group consisting of Direct Yellow 142

Magenta dye (M-1): Dye represented by formula (M-1) Magenta dye (M-2): Dye represented by formula (M-2a), Dye represented by formula (M-2b) , C.I. I. Acid Red 1 and C.I. I. At least one dye selected from the group consisting of Acid Red 254

Cyan dye (C-1): Dye represented by formula (C-1)

In the formula (Y-1),
R ₁ , R ₂ , Y ₁ and Y ₂ are each a monovalent group, and R ₁ , R ₂ , Y ₁ and Y ₂ may be the same or different,
X ₁ and X ₂ are each an electron-withdrawing group, and X ₁ and X ₂ may be the same or different,
Z ₁ and Z ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, A cyclic group, Z ₁ and Z ₂ may be the same or different;
M ₁ is a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group).

In the formula (M-1),
n ₁ is 1 or 2,
The three M's are each sodium or NH ₄ , and the three M's may be the same or different;
R ₀ is a monoalkylamino group having 1 to 8 carbon atoms substituted with a carboxy group.

In the formula (M-2a),
R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
R ₁₂ is a hydrogen atom, a halogen atom or a cyano group,
R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted sulfonyl group. A substituted or unsubstituted acyl group, and R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different, but R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ is not both a hydrogen atom,
A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one is a substituted or unsubstituted carbon atom and the other is a carbon atom.

In formula (M-2b),
r is 0, 1 or 2;
R ₁₈ , R ₁₉ and R ₂₀ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. A sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a carboxy group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, substituted or unsubstituted It is an unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.

In formula (C-1),
Rings A ₃₁ , A ₃₂ and A ₃₃ are at least one selected from the group consisting of a benzene ring, a 2,3-pyridine ring and a 3,2-pyridine ring, respectively, and the rings A ₃₁ , A ₃₂ And at least one of A ₃₃ is a 2,3-pyridine ring or a 3,2-pyridine ring, and the rings A ₃₁ , A ₃₂ and A ₃₃ may be the same or different,
a satisfies 0 ≦ a ≦ 4, b satisfies 0 ≦ b ≦ 4, c satisfies 0 ≦ c ≦ 4, and a, b, and c satisfy 0 ≦ a + b + c ≦ 4,
z is an integer satisfying 1 ≦ z ≦ 3,
R ₃₀ is a linear alkylene group having 1 to 6 carbon atoms. 6. The inkjet recording method according to claim 5, wherein in the composite black forming step, composite black is formed on glossy paper so as to satisfy the following condition (A2).

(A2) 0.75 ≦ M / (Y + C)
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the yellow dye (Y-1) and the yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the magenta dye (M-1) and the magenta dye (M-2)
C: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the cyan dye (C-1)
The total amount of the yellow dye (Y-1) and the yellow dye (Y-2) is 2% by weight to 6% by weight with respect to the total amount of the water-based yellow ink,
The total amount of the magenta dye (M-1) and the magenta dye (M-2) is 2% by weight to 6% by weight with respect to the total amount of the water-based magenta ink.
The ink jet recording method according to claim 5 or 6, wherein the amount of the cyan dye (C-1) is 2 wt% to 7 wt% with respect to the total amount of the cyan ink. The inkjet recording method according to any one of claims 5 to 7, wherein the glossy paper is a glossy paper having a void type resin coat layer. A recorded matter recorded by the ink jet recording method according to claim 5. A composite black formed on glossy paper using the following aqueous yellow ink, aqueous magenta ink and aqueous cyan ink so as to satisfy the following conditions (A) and (B).

(A) 0.68 ≦ M / (Y + C)
(B) 500 ≦ Y + M + C ≦ 600
Y: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following yellow dye (Y-1) and yellow dye (Y-2)
M: Drop amount (ng) of glossy paper 25.4 mm × 25.4 mm of the following magenta dye (M-1) and magenta dye (M-2)
C: Drip amount (ng) per glossy paper 25.4 mm × 25.4 mm of the following cyan dye (C-1)

Water-based yellow ink: Water-based ink containing the following yellow dye (Y-1) and yellow dye (Y-2)

Water-based magenta ink: Water-based ink containing the following magenta dye (M-1) and magenta dye (M-2)

Water-based cyan ink: Water-based ink containing the following cyan dye (C-1)

Yellow dye (Y-1): Dye represented by formula (Y-1) Yellow dye (Y-2): C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 132 and C.I. I. At least one dye selected from the group consisting of Direct Yellow 142

Magenta dye (M-1): Dye represented by formula (M-1) Magenta dye (M-2): Dye represented by formula (M-2a), Dye represented by formula (M-2b) , C.I. I. Acid Red 1 and C.I. I. At least one dye selected from the group consisting of Acid Red 254

Cyan dye (C-1): Dye represented by formula (C-1)

In the formula (Y-1),
R ₁ , R ₂ , Y ₁ and Y ₂ are each a monovalent group, and R ₁ , R ₂ , Y ₁ and Y ₂ may be the same or different,
X ₁ and X ₂ are each an electron-withdrawing group, and X ₁ and X ₂ may be the same or different,
Z ₁ and Z ₂ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero group, A cyclic group, Z ₁ and Z ₂ may be the same or different;
M ₁ is a hydrogen atom, an alkali metal atom, NH ₄ or NR ₄ (R is an alkyl group or an aryl group).

In the formula (M-1),
n ₁ is 1 or 2,
The three M's are each sodium or NH ₄ , and the three M's may be the same or different;
R ₀ is a monoalkylamino group having 1 to 8 carbon atoms substituted with a carboxy group.

In the formula (M-2a),
R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
R ₁₂ is a hydrogen atom, a halogen atom or a cyano group,
R ₁₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,
R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted sulfonyl group. A substituted or unsubstituted acyl group, and R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be the same or different, but R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ is not both a hydrogen atom,
A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one is a substituted or unsubstituted carbon atom and the other is a carbon atom.

In formula (M-2b),
r is 0, 1 or 2;
R ₁₈ , R ₁₉ and R ₂₀ are each a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. A sulfamoyl group, a substituted or unsubstituted amino group, a nitro group, a sulfonic acid ester group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a carboxy group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alicyclic group, substituted or unsubstituted It is an unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.

In formula (C-1),
Rings A ₃₁ , A ₃₂ and A ₃₃ are at least one selected from the group consisting of a benzene ring, a 2,3-pyridine ring and a 3,2-pyridine ring, respectively, and the rings A ₃₁ , A ₃₂ And at least one of A ₃₃ is a 2,3-pyridine ring or a 3,2-pyridine ring, and the rings A ₃₁ , A ₃₂ and A ₃₃ may be the same or different,
a satisfies 0 ≦ a ≦ 4, b satisfies 0 ≦ b ≦ 4, c satisfies 0 ≦ c ≦ 4, and a, b, and c satisfy 0 ≦ a + b + c ≦ 4,
z is an integer satisfying 1 ≦ z ≦ 3,
R ₃₀ is a linear alkylene group having 1 to 6 carbon atoms.

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