JP5522502B2 - Ink set for ink jet recording, ink cartridge, and ink jet recording apparatus - Google Patents

Description

  The present invention relates to an ink set for ink jet recording, an ink cartridge, and an ink jet recording apparatus.

  2. Description of the Related Art Conventionally, ink sets including yellow ink, magenta ink, and cyan ink containing a colorant, water, and a water-soluble organic solvent have been widely used as ink sets for inkjet recording. When a color image recorded using such an ink set fades with time, the color image may change significantly from the image immediately after recording. In order to solve this problem, there has been proposed an ink set in which inks having different color fading rates in order of brightness are combined (Patent Document 1). This ink set makes it difficult to visually recognize fading and can improve the light resistance of the obtained image apparently. However, this ink set does not improve the light resistance of each color ink itself, and thus the light resistance of the recorded matter is not sufficient.

JP 2000-178491 A

  Accordingly, an object of the present invention is to provide an ink set for ink-jet recording that has excellent fastness such as light resistance and ozone resistance of a recorded matter, and has little change in color balance of an image even if the color fades. .

前記一般式（Ｙ−１）において、
Ｒ_１、Ｒ_２、Ｙ_１およびＹ_２は、それぞれ、一価の基であり、Ｒ_１、Ｒ_２、Ｙ_１およびＹ_２は同一でも異なっていてもよく、
Ｘ_１およびＸ_２は、それぞれ、電子吸引性基であり、Ｘ_１およびＸ_２は同一でも異なっていてもよく、
Ｚ_１およびＺ_２は、それぞれ、水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアラルキル基、置換または無置換のアリール基、置換または無置換のヘテロ環基であり、Ｚ_１およびＺ_２は同一でも異なっていてもよく、
Ｍ_１は、水素原子またはカチオンである。

前記一般式（Ｍ−１）において、
Ｒ_１１は、水素原子、置換または無置換のアルキル基、置換または無置換のアリール基であり、
Ｒ_１２は、水素原子、ハロゲン原子またはシアノ基であり、
Ｒ_１３は、水素原子、置換または無置換のアルキル基、置換または無置換のアリール基、置換または無置換のヘテロ環基であり、
Ｒ_１４、Ｒ_１５、Ｒ_１６およびＲ_１７は、それぞれ、水素原子、置換または無置換のアルキル基、置換または無置換のアリール基、置換または無置換のヘテロ環基、置換または無置換のスルホニル基、置換または無置換のアシル基であり、Ｒ_１４、Ｒ_１５、Ｒ_１６および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およびＡ_２は、双方が置換または無置換の炭素原子であるか、若しくは一方が置換または無置換の炭素原子であり、且つ、他方が窒素原子である。

前記一般式（Ｃ−１）において、
Ｐｃ（Ｃｕ）は、下記一般式（Ｐｃ）で表される銅フタロシアニン核であり、
Ｒ_３１、Ｒ_３２、Ｒ_３３およびＲ_３４は、それぞれ、−ＳＯ_２Ｒ_ａ、−ＳＯ_２ＮＲ_ｂＲ_ｃおよび−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およびＲ_３４のすべてが同一であることはなく、Ｒ_３１、Ｒ_３２、Ｒ_３３および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およびＲ_３４の少なくとも一つは、一般式（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およびＤのそれぞれに存在し、Ｒ_ａは、置換または無置換のアルキル基であり、Ｒ_ｂは、水素原子、置換または無置換のアルキル基であり、Ｒ_ｃは、置換または無置換のアルキル基であり、
ｋは、０＜ｋ＜８を満たす整数であり、ｌは、０＜ｌ＜８を満たす整数であり、ｍは、０≦ｍ＜８を満たす整数であり、ｎは、０≦ｎ＜８を満たす整数であり、且つ、ｋ、ｌ、ｍおよびｎは、４≦ｋ＋ｌ＋ｍ＋ｎ≦８を満たす整数である。

前記一般式（Ｃ−２）において、
Ｐｃ（Ｃｕ）は、前記一般式（Ｐｃ）で表される銅フタロシアニン核であり、
ｓは、０＜ｓ＜４を満たす整数であり、ｔは、０≦ｔ＜４を満たす整数であり、且つ、ｓおよびｔは、２≦ｓ＋ｔ≦５を満たす整数である。
ＳＯ_３Ｍ_２基は、一般式（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およびＤのいずれかに存在し、
ｔ≠０において、ＳＯ_２ＮＨ_２基は、一般式（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およびＤのいずれかに存在し、
Ｍ_２は、リチウムイオン、ナトリウムイオン、カリウムイオンまたはアンモニウムイオンである。

前記一般式（１）において、ｐおよびｑは同一でも異なっていてもよく、ｐ＋ｑ＝１〜１５を満たす数であり、
Ｒ_４１、Ｒ_４２、Ｒ_４３およびＲ_４４は、それぞれ同一でも異なっていてもよく、炭素原子数１〜５の直鎖状または分岐鎖状アルキル基である。 In order to achieve the above object, the ink set for inkjet recording of the present invention comprises:
An ink set for inkjet recording containing yellow ink, magenta ink and cyan ink,
The yellow ink contains a yellow colorant, water and a water-soluble organic solvent, the yellow colorant is a dye (Y-1) represented by the following general formula (Y-1), and the water-soluble organic solvent is multivalent. Including alcohol;
The magenta ink contains a magenta colorant, water, a water-soluble organic solvent, and an acetylene glycol surfactant, and the magenta colorant is a dye (M-1) represented by the following general formula (M-1), The water-soluble organic solvent contains dipropylene glycol propyl ether, the acetylene glycol surfactant contains a surfactant represented by the following general formula (1), and the dipropylene glycol propyl ether and the general formula (1) Are blended so as to satisfy the following conditions (i) and (ii) respectively:

(I) 0.5 ≦ x ≦ 2.5
(Ii) 1 ≦ y ≦ 3
x: blending amount (wt%) of the surfactant represented by the general formula (1) with respect to the total amount of magenta ink
y: blending amount of dipropylene glycol propyl ether with respect to the total amount of magenta ink (% by weight)

The cyan ink contains a cyan colorant, water, and a water-soluble organic solvent, and the cyan colorant is represented by the following general formula (C-1) (C-1) and the following general formula (C-2). A dye (C-2) represented by
In the yellow ink, the polyhydric alcohol is glycerin, and the blending ratio of the dye (Y-1) and glycerin is set to satisfy the following condition (iv ′):

(Iv ′) Y2 ≦ 3.5X
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (% by weight)

In the magenta ink, the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) are further blended so as to satisfy the following condition (v) :

(V) y ≧ −2x + 3 and y ≦ −2x + 6
x: blending amount (wt%) of the surfactant represented by the general formula (1) with respect to the total amount of magenta ink
y: blending amount of dipropylene glycol propyl ether with respect to the total amount of magenta ink (% by weight)

The weight ratio of the at cyan ink dye (C-1) and the dye (C-2) is a dye (C-1): Dye (C-2) = 70: 30~95: 5 der Rukoto It is characterized by.

In the general 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 aralkyl group, substituted or unsubstituted aryl A substituted or unsubstituted heterocyclic group, Z ₁ and Z ₂ may be the same or different;
M ₁ is a hydrogen atom or a cation.

In the general formula (M-1),
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 nitrogen atom.

In the general formula (C-1),
Pc (Cu) is a copper phthalocyanine nucleus represented by the following general 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 , R ₃₃ and R ₃₄ are present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc), and R _a is substituted or An unsubstituted alkyl group, R _b is a hydrogen atom, a substituted or unsubstituted alkyl group, R _c is a substituted or unsubstituted alkyl group,
k is an integer satisfying 0 <k <8, l is an integer satisfying 0 <l <8, m is an integer satisfying 0 ≦ m <8, and n is 0 ≦ n <8 And k, l, m and n are integers satisfying 4 ≦ k + 1 + m + n ≦ 8.

In the general formula (C-2),
Pc (Cu) is a copper phthalocyanine nucleus represented by the general formula (Pc),
s is an integer that satisfies 0 <s <4, t is an integer that satisfies 0 ≦ t <4, and s and t are integers that satisfy 2 ≦ s + t ≦ 5.
The SO ₃ M ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc),
At t ≠ 0, the SO ₂ NH ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc);
M ₂ is a lithium ion, a sodium ion, a potassium ion or an ammonium ion.

In the general formula (1), p and q may be the same or different, and are numbers satisfying p + q = 1 to 15,
R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ may be the same or different, and are each a linear or branched alkyl group having 1 to 5 carbon atoms.

  In the ink set of the present invention, the yellow ink, the magenta ink, and the cyan ink contain the dye (Y-1), the dye (M-1), and the dye (C-1), respectively. Excellent in properties. Furthermore, even if the ink set of the present invention fades, the color fading of the inks of the respective colors is almost the same, so that there is little change in the color balance of the image.

In the yellow ink constituting the ink set for ink jet recording of the present invention, the polyhydric alcohol is glycerin, and the blending ratio of the dye (Y-1) and glycerin satisfies the following condition (iv ′). Is set . In the yellow ink constituting the ink set for inkjet recording of the present invention, the blending ratio of the dye (Y-1) and glycerin is set so as to satisfy the following condition (iv ″). preferable.

(Iv ′) Y2 ≦ 3.5X
(Iv ′) 3.5X−5 ≦ Y2
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (% by weight)

In the yellow ink containing the dye (Y-1), if the blending ratio of glycerin is set so as to satisfy the condition (iv ′), a yellow ink having excellent storage stability and ejection stability can be obtained. . In addition, in the yellow ink containing the dye (Y-1), if the blending ratio of glycerin is set so as to satisfy the condition (iv ″) , a yellow ink having superior storage stability and ejection stability can be obtained. be able to. Such an improvement in performance has been found for the first time by the present inventors. The mechanism by which the yellow ink is excellent in storage stability and ejection stability is assumed as follows , for example. Since the dye (Y-1) has a triazine skeleton with extremely high hydrogen bonding properties, for example, when the yellow ink contains a solvent having a hydroxyl group, the dye (Y-) is brought into contact with the solvent when stored for a long period of time. Part of 1) may be decomposed. On the other hand, among the solvents containing a hydroxyl group, the yellow ink particularly selects glycerin and contains the glycerin at a blending ratio that satisfies the condition of Y2 ≦ 3.5X. ) Is suppressed. In addition, for example, when the dye (Y-1) is used in combination with a pigment ink in an ink set for inkjet recording, the dye (Y-1) is likely to aggregate due to contact with the pigment ink. When the agglomeration occurs, for example, the agglomerate may adhere to the nozzles of the ink jet head, which may cause ink ejection bending. In addition, the aggregate may be clogged with a maintenance mechanism of the ink jet recording apparatus. On the other hand, for example, when the yellow ink is used in combination with a pigment ink, the blending ratio of the glycerin is set to satisfy the condition of Y2 ≧ 3.5X-5. Is suppressed. These performance improvement mechanisms are speculations and do not limit the present invention.

In the yellow ink, when X> 5 / 3.5, the dye (Y-1) and glycerin are mixed in the yellow ink at a blending ratio that satisfies the conditions (iv ′) and (iv ″). Included,
In the case of X ≦ 5 / 3.5, the dye (Y-1) and glycerin may be contained in the yellow ink at a blending ratio that satisfies the following condition (vii).

(Vii) 0 <Y2 ≦ 3.5X
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (% by weight)

  In the yellow ink, when X ≦ 5 / 3.5, glycerin may not be contained in the yellow ink. As described above, when the blending ratio of the dye (Y-1) is small, the agglomeration hardly occurs even when glycerin is not included, and a yellow ink that is excellent in ejection stability can be obtained.

  In the yellow ink constituting the ink set for ink jet recording of the present invention, the amount of the dye (Y-1) is preferably 1 to 5% by weight based on the total amount of the yellow ink.

In the yellow ink constituting the ink set for inkjet recording of the present invention, the yellow colorant further contains the following dye (Y-2), and the dye (Y-1) and the dye (Y in the yellow ink) -2) is preferably dye (Y-1): dye (Y-2) = 70: 30 to 90:10.
Dye (Y-2): C.I. I. Direct Yellow 86 and C.I. I. By using a combination of at least one of the direct yellow 132, the dye (Y-1) and the dye (Y-2), it is possible to obtain a yellow ink that is superior in color developability. Such an improvement in performance has been found for the first time by the present inventors.

  In the yellow ink constituting the ink set for inkjet recording of the present invention, the total blending amount of the dye (Y-1) and the dye (Y-2) is 1.1 to 7 with respect to the total amount of the yellow ink. It is preferably 1% by weight.

  As described above, in the magenta ink constituting the ink set for ink jet recording of the present invention, the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) are the above (i) and (ii), respectively. ) So as to satisfy the above condition. For this reason, the magenta ink is excellent in ejection stability and print quality, and the compound derived from the material forming the ink jet recording apparatus is prevented from being eluted into the ink. Examples of the material forming the ink jet recording apparatus include a rubber member and an organic material member other than the rubber material. Examples of the rubber member include a wiper and a cap. For example, the wiper wipes the nozzle surface of the inkjet head. For example, the cap blocks the nozzle surface and the outside world. When the compound derived from the material forming the ink jet recording apparatus elutes into the ink, the compound may precipitate in the ink. When the compound is precipitated, for example, the nozzle of the inkjet head may be clogged.

  The inventors have found for the first time an improvement in the performance of the magenta ink constituting the ink set for ink jet recording of the present invention as described above. The mechanism by which the magenta ink is excellent in the performance is assumed as follows, for example. The magenta ink containing the dye (M-1) has a problem in ejection stability when used for a long period of time, for example. In contrast, the magenta ink is formulated so that the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) satisfy the conditions (i) and (ii). Even when used for a long period of time, the jetting stability is excellent, the printing quality is excellent, and further, the elution of the compound derived from the rubber member or the like in the ink jet recording apparatus into the ink is prevented. These performance improvement mechanisms are speculations and do not limit the present invention.

  In the magenta ink constituting the ink jet recording ink set of the present invention, the amount of the dye (M-1) is preferably 1 to 5% by weight based on the total amount of the magenta ink.

前記一般式（Ｍ−２ａ）において、
Ｒ_１８、Ｒ_１９およびＲ_２０は、それぞれ、置換または無置換のアルキル基、置換また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、置換または無置換のカルバモイル基、置換または無置換のスルファモイル基、置換または無置換のアミノ基、ニトロ基、スルホン酸エステル基、置換または無置換のアルキルスルホニル基、置換または無置換のアリールスルホニル基、カルボキシル基、カルボン酸エステル基であり、Ｒ_１８、Ｒ_１９およびＲ_２０は同一でも異なっていてもよく、
ｒは、０、１または２であり、
Ｒ_２１、Ｒ_２２およびＲ_２３は、それぞれ、水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアリール基、置換または無置換のアラルキル基、置換または無置換の脂環基、置換または無置換のヘテロ環基であり、Ｒ_２１、Ｒ_２２およびＲ_２３は同一でも異なっていてもよい。
前記染料（Ｍ−１）と前記染料（Ｍ−２）とを組み合わせて用いることで、発色性により優れたマゼンタインクを得ることができる。このような性能の向上は、本発明者等が初めて見出したものである。 In the magenta ink constituting the ink set for inkjet recording of the present invention, the magenta colorant further contains the following dye (M-2), and the dye (M-1) and the dye (M -2) is preferably dye (M-1): dye (M-2) = 70: 30 to 90:10.
Dye (M-2): Dye (M-2a) whose free acid is represented by the following general formula (M-2a), C.I. I. Acid Red 52 and C.I. I. At least one dye selected from the group consisting of Acid Red 289

In the general formula (M-2a),
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 carboxyl group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
r is 0, 1 or 2;
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 aralkyl group, substituted or unsubstituted It is a substituted alicyclic group, a substituted or unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.
By using the dye (M-1) and the dye (M-2) in combination, it is possible to obtain a magenta ink that is more excellent in color developability. Such an improvement in performance has been found for the first time by the present inventors.

  In the magenta ink constituting the ink set for inkjet recording of the present invention, the total blending amount of the dye (M-1) and the dye (M-2) is 1.1 to 7 with respect to the total amount of the magenta ink. It is preferably 1% by weight.

  As described above, the cyan ink constituting the ink set for inkjet recording of the present invention includes the dye (C-1) and the dye (C-2). For this reason, the cyan ink has excellent color developability, ozone resistance and light resistance.

  The inventors have found for the first time an improvement in the performance of the cyan ink constituting the ink set for ink jet recording of the present invention as described above. The mechanism by which the cyan ink is excellent in the performance is estimated as follows, for example. The dye (C-1) is excellent in ozone resistance and light resistance. On the other hand, the dye (C-2) is excellent in color developability. These performance improvement mechanisms are speculations and do not limit the present invention.

  In the cyan ink constituting the ink set for ink jet recording of the present invention, the amount of the dye (C-1) is preferably 1 to 5% by weight with respect to the total amount of the cyan ink.

  In the cyan ink constituting the ink set for inkjet recording of the present invention, the total blending amount of the dye (C-1) and the dye (C-2) is 1.1 to 7 with respect to the total amount of the cyan ink. It is preferably 1% by weight.

  The ink cartridge of the present invention is an ink cartridge having storage portions for yellow ink, magenta ink, and cyan ink, respectively, and the yellow ink, the magenta ink, and the cyan ink form the ink set for ink jet recording of the present invention. It is characterized by being composed of yellow ink, magenta ink, and cyan ink.

  The ink jet recording apparatus of the present invention is an ink jet recording apparatus that includes an ink cartridge and an ink discharge means, and ink for ink jet recording is discharged from the ink discharge means, and the ink cartridge is the ink cartridge of the present invention. It is characterized by that.

  Next, the ink set for inkjet recording of the present invention will be described. The ink set of the present invention includes yellow ink, magenta ink, and cyan ink.

(Yellow ink)
First, the yellow ink will be described. As described above, the yellow ink includes a yellow colorant, water, and a water-soluble organic solvent. The yellow colorant contains the dye (Y-1).

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

In the general 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. Good. 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.

  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.

  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 methyl group, ethyl group, butyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, hydroxyethyl group, cyanoethyl group, 4-sulfobutyl group and the like. . 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, a 2-methylsulfonylethyl group, and a 3-phenoxypropyl group. A linear or branched alkyl group having 1 to 12 carbon atoms such as a group or a trifluoromethyl group; a linear or branched aralkyl group having 7 to 18 carbon atoms; a linear or branched chain having 2 to 12 carbon atoms An 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 or branched chain having 3 to 12 carbon atoms; Cycloalkenyl group; halogen atom such as chlorine atom and bromine atom; phenyl group, 4-tert-butylphenyl group, 2,4-di-tert-amyl Aryl groups such as phenyl groups; heterocyclic groups such as imidazolyl groups, pyrazolyl groups, triazolyl groups, 2-furyl groups, 2-thienyl groups, 2-pyrimidinyl groups, 2-benzothiazolyl groups; cyano groups; hydroxyl groups; nitro groups; 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 Groups, aryloxy groups such as 3-tert-butyloxycarbonylphenoxy group, 3-methoxycarbonylphenyloxy group; acylamino groups such as acetamide group, benzamide group, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide group Group: Methylamino group, Butyla Alkylamino groups such as phenyl group, diethylamino 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; Sulfamoylamino groups such as N, N-dipropylsulfamoylamino group; alkylthio groups such as methylthio group, octylthio group and 2-phenoxyethylthio group; phenylthio group, 2-butoxy-5-tert-octylphenylthio group Arylthio groups such as 2-carboxyphenylthio group; alkoxycarbonylamino groups such as methoxycarbonylamino group; alkylsulfonylamino groups such as methylsulfonylamino group; arylsulfonylamino groups such as phenylsulfonylamino group and p-toluenesulfonylamino group Carbamoyl groups such as N-ethylcarbamoyl group and N, N-dibutylcarbamoyl group; sulfamoyl groups such as N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group and N-phenylsulfamoyl group Sulfonyl groups such as methylsulfonyl group, octylsulfonyl group, phenylsulfonyl group and p-toluenesulfonyl group; alkoxycarbonyl groups such as methoxycarbonyl group and butyloxycarbonyl group; 1-phenyltetrazole-5-oxy group and 2-tetrahydro group; Heterocyclic oxy groups such as pyranyloxy groups; azo groups such as phenylazo groups, 4-methoxyphenylazo groups, 4-pivaloylaminophenylazo groups, 2-hydroxy-4-propanoylphenylazo groups; acetoxy groups, etc. An acyloxy group of N-methylcarbamoyloxy Carbamoyloxy groups such as tri- and N-phenylcarbamoyloxy groups; silyloxy groups such as trimethylsilyloxy groups and dibutylmethylsilyloxy groups; aryloxycarbonylamino groups such as phenoxycarbonylamino groups; N-succinimide groups and N-phthalimide groups Imido groups such as 2-benzothiazolylthio group, 2,4-di-phenoxy-1,3,5-triazole-6-thio group, 2-pyridylthio group and other heterocyclic thio groups; 3-phenoxypropylsulfinyl Sulfinyl groups such as groups; phosphonyl groups such as phenoxyphosphonyl groups, octyloxyphosphonyl groups and phenylphosphonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acetyl groups, 3-phenylpropanoyl groups, benzoyl groups, etc. Acyl group; carboxyl group Sulfo group, a phosphono group, such as an ionic hydrophilic group such as a 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, are from the viewpoint of improving the solubility of the dye and the stability of the ink. 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 hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt), and a carboxyl group (may be in the form of a salt).

  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.

  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.

  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.

  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.

  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.

  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, and these are further condensed. Also good. 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. Examples of the heterocyclic group include, but are not limited to, substitution positions such as 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, benz Examples include isothiazole group, thiadiazole group, isoxazole group, benzisoxazole group, pyrrolidine group, piperidine group, piperazine group, imidazolidine group, thiazoline group and the like.

  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.

  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.

  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.

  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.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. 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.

  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.

  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.

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

  The amino group is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms and 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 those exemplified as the substituent 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.

  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 arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the substituent of the substituted alkylcarbonylamino group and the substituted arylcarbonylamino group include the same substituents as those exemplified as the substituent 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.

  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 the same substituents as the substituents of 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.

  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.

  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.

  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.

  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.

  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.

  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-hexadecylthio group.

  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.

  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.

  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.

  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.

  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-methylphenylsulfinyl group.

  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.

  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.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a 4 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom. Examples of the substituent of the substituted alkylcarbonyl group, the substituted arylcarbonyl group, and the 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-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, and a 2-furylcarbonyl group. It is done.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the substituent of the substituted 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.

  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.

  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.

  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.

  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.

  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 substituted alkyl group. Examples of the phosphinyloxy group include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. Examples of the substituent of the substituted 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.

  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.

  Examples of the azo group include a phenylazo group, a 4-methoxyphenylazo group, a 4-pivaloylaminophenylazo group, a 2-hydroxy-4-propanoylphenylazo group, and the like.

  Examples of the imide group include an N-succinimide group and an N-phthalimide group.

In the general 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.

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, or an alkoxycarbonyl having 2 to 12 carbon atoms. Group, aryloxycarbonyl group having 7 to 18 carbon atoms, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkyl having 1 to 12 carbon atoms Sulfonyl group, arylsulfonyl group having 6 to 18 carbon atoms, sulfamoyl group having 0 to 12 carbon atoms, halogenated alkyl group having 1 to 12 carbon atoms, halogenated alkoxy group having 1 to 12 carbon atoms, carbon atom A halogenated alkylthio group having 1 to 12 carbon atoms, a halogenated aryloxy group having 7 to 18 carbon atoms, and two or more other electron-withdrawing groups Substituted aryl group having a carbon number of 7 to 18, a nitrogen atom, an oxygen atom or a heterocyclic group having 1 to 18 carbon atoms in the 5- to 8-membered ring having a sulfur atom.

In the general 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, substituted or unsubstituted An aralkyl group, a substituted or unsubstituted aryl 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 aralkyl group, the aryl group, and the heterocyclic group are the same as those in R ₁ , R ₂ , Y _1, and Y ₂ .

In the general formula (Y-1), M ₁ is a hydrogen atom or a cation. The cation is an alkali metal ion, an ammonium ion, or a quaternary ammonium ion. The cation is preferably Li, Na, K, NH ₄ , or NR ₄ . Here, R in R ₄ is an alkyl group or an aryl group, and is the same as in R ₁ , R ₂ , Y ₁ and Y ₂ . Among these, the cation, Li, Na, K, is preferably NH _4.

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

  Particularly preferable combinations of substituents of the dye represented by the general 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 in total, or a substituted or unsubstituted carbon atom having 6 to 18 carbon atoms in total. 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, more preferably secondary or A tertiary alkyl group, 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 or 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 carbon atom having 6 to 18 carbon atoms in total. An aryl group, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, 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 ion, an ammonium ion, or a quaternary ammonium ion, and more preferably a hydrogen atom, Li, Na, K, or NH ₄ .

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

  The compounding amount of the dye (Y-1) is not particularly limited. By including the dye (Y-1) in the yellow ink, the fastness of the recorded matter using the yellow ink can be improved. As described above, the blending amount of the dye (Y-1) is preferably 1 to 5% by weight with respect to the total amount of the yellow ink.

  The yellow colorant may be composed only of the dye (Y-1), and may further contain other dyes and pigments.

  The water is preferably ion exchange water or pure water. The blending amount of the water with respect to the total amount of the ink is, for example, 10 to 90% by weight, and preferably 40 to 80% by weight. The blending amount of water may be, for example, the balance of other components.

  The water-soluble organic solvent is classified into, for example, a wetting agent that prevents the ink from drying at the tip of the ink jet head and a penetrating agent that adjusts the drying speed on the recording paper surface.

The yellow ink contains a polyhydric alcohol as the wetting agent. The polyhydric alcohol is glycerin.

  The wetting agent may be composed only of the polyhydric alcohol, or may further contain another wetting agent.

The wetting agent other than the polyhydric alcohol is not limited, for example, lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; Amides such as formamide and dimethylacetamide; Ketones such as acetone; Keto alcohols such as diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Polyethers such as polyalkylene glycol; 2-pyrrolidone; N-methyl-2-pyrrolidone; 3-dimethyl-2-imidazolidinone and the like. The polyalkylene glycol is not limited, and examples thereof include polyethylene glycol and polypropylene glycol. One type of wetting agent other than the polyhydric alcohol may be used, or two or more types may be used.

  The blending amount of the wetting agent is not particularly limited. The blending amount of the wetting agent with respect to the total amount of the yellow ink is, for example, 0 to 95% by weight, preferably 10 to 80% by weight, and more preferably 10 to 50% by weight.

  The penetrant is not limited, and examples thereof include glycol ethers. The glycol ether is not limited, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, triethylene glycol methyl ether, triethylene. Glycol ethyl ether, triethylene glycol propyl ether, triethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether Ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether and tripropylene glycol butyl ether, and the like. The said penetrant may be used individually by 1 type, and may use 2 or more types together.

  The blending amount of the penetrant is, for example, 0 to 20% by weight. By setting the blending amount of the penetrant within the above range, the penetrability of the yellow ink into paper can be further improved. The blending amount of the penetrant is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight.

  The yellow ink may further contain a conventionally known additive as required. Examples of the additive include a surfactant, a viscosity modifier, a surface tension modifier, and an antifungal agent. The viscosity modifier is not limited, and examples thereof include polyvinyl alcohol, cellulose, and a water-soluble resin.

  The yellow ink is prepared by, for example, uniformly mixing a yellow colorant, water, a water-soluble organic solvent, and, if necessary, other additive components by a conventionally known method, and removing insoluble matters with a filter. Can be prepared.

  Next, preferred specific examples of the yellow ink will be described. However, the yellow ink is not limited to these examples.

(The first of the yellow ink)
In the yellow ink of this example, the polyhydric alcohol is glycerin, and in the yellow ink, the blending ratio of the dye (Y-1) and glycerin is set so as to satisfy the following condition (iv ″). ing.

(Iv ″) 3.5X−5 ≦ Y2
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (% by weight)

The mixing ratio of glycerin is, that is set so as to satisfy the condition of Y2 ≧ 3.5X-5, it is possible to obtain an excellent yellow ink by ejection stability.

  In the yellow ink of this example, when X ≦ 5 / 3.5, glycerin may not be contained in the yellow ink. Thus, when there are few compounding ratios of the said dye (Y-1), even if it does not contain glycerol, the said aggregation is hard to occur and the ink excellent in discharge stability can be obtained.

  The composition of the yellow ink of this example other than these is as described above. However, in the yellow ink of this example, the blending amount of the water-soluble organic solvent other than glycerin is preferably in a range that does not impair the effects obtained by including glycerin.

( Second yellow ink)
In the yellow ink of this example, the yellow colorant contains the following dye (Y-2) in addition to the dye (Y-1).
Dye (Y-2): C.I. I. Direct Yellow 86 and C.I. I. At least one of Direct Yellow 132

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

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

  In the yellow ink of this example, the blending amount of the dye (Y-2) is not particularly limited. By including the dye (Y-2) in the yellow ink, the color developability can be improved. The blending amount of the dye (Y-2) is, for example, 0.1 to 2.1% by weight, preferably 0.3 to 1.1% by weight, based on the total amount of the yellow ink in this example.

  The weight ratio of the dye (Y-1) and the dye (Y-2) in the yellow ink of this example is dye (Y-1): dye (Y-2) = 70: 30 to 90:10. It is preferable. By setting the weight ratio within the above range, it is possible to obtain a yellow ink that is more excellent in color developability. The weight ratio is more preferably dye (Y-1): dye (Y-2) = 80: 20 to 90:10.

  In the yellow ink of this example, the total amount of the dye (Y-1) and the dye (Y-2) is not particularly limited, but is 1.1 to 7.1% by weight based on the total amount of the yellow ink. And more preferably 2 to 4% by weight.

  The composition of the yellow ink of this example other than these is as described above.

(Magenta ink)
Next, the magenta ink will be described. As described above, the magenta ink includes a magenta colorant, water, a water-soluble organic solvent, and an acetylene glycol surfactant. The magenta colorant contains the dye (M-1).

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

As described above, in the general formula (M-1),
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 nitrogen atom.

  In the general formula (M-1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the general formula (M-1), 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 general formula (M-1), 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 general formula (M-1), 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 -A sulfonate benzothiazolyl group and the like. 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 general formula (M-1), 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 a substituted or unsubstituted alkyl group similar to the above, a substituted or unsubstituted aryl group similar to the above.

  In the general formula (M-1), 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 the general formula (M-1), as described above, A ₁ and A ₂ are both substituted or unsubstituted carbon atoms, or one of them is a substituted or unsubstituted carbon atom, and the other Is a nitrogen 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 a carbon atom of A ₁ and A _2, for example, an alkyl group having 1 to 3 carbon atoms, a carboxyl group, a carbamoyl group, a cyano group, and the like.

As described above, in the general formula (M-1), R ₁₄ and R ₁₅ are not both hydrogen atoms, and R ₁₆ and R ₁₇ are not both hydrogen atoms. In the general formula (M-1), if the number of substitutions of the sulfonic acid group or carboxyl group increases, the water solubility of the dye (M-1) tends to be improved. Is preferably adjusted.

As a preferable embodiment of the dye (M-1), for example, in the general formula (M-1), R ₁₁ is an alkyl group, R ₁₂ is a cyano group, R ₁₃ is a hydrogen atom or a substituted or unsubstituted heterocycle. A group, R ₁₄ is a hydrogen atom, a substituted or unsubstituted heterocyclic group or a substituted aryl group, R ₁₅ and R ₁₆ are each a substituted heterocyclic group or a substituted aryl group, R ₁₇ is a hydrogen atom, and A ₁ is An embodiment in which the substituted carbon atom and A ₂ is a substituted or unsubstituted carbon atom is exemplified.

As a more preferable embodiment of the dye (M-1), for example, in the general formula (M-1), 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 benzothiazolyl group (preferably a benzothiazol-2-yl group) optionally substituted with the alkali metal base, and a benzothiazolyl group (preferably R ₁₄ ) optionally substituted with a hydrogen atom, a sulfonic acid group or the alkali metal base Benzothiazol-2-yl group) or a trialkylphenyl group (preferably a mesityl group) substituted with a sulfonic acid group or an alkali metal base thereof, R ₁₅ and R ₁₆ are each a sulfonic acid group or an alkali thereof. Mono-, di- or trialkylphenyl groups (preferably substituted with metal bases) , 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 This is an embodiment in which a carbon atom substituted with an alkyl group (preferably a methyl group) and A ₂ is a carbon atom optionally substituted with a cyano group.

  Preferable specific examples of the dye (M-1) include compounds represented by the following chemical formulas (M-1a) to (M-1f).

In the compound represented by the chemical formula (M-1a), in the general formula (M-1), 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 p-octylphenyl groups, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is a carbon atom substituted with a cyano group This is an embodiment.

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

The compound represented by the chemical formula (M-1c) is the compound represented by the general formula (M-1), wherein R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are 6-sulfo sodium salt benzo A thiazol-2-yl group, R ₁₅ and R ₁₆ are 3-sulfosodium salt-mesityl groups, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is a carbon atom It is an aspect.

In the compound represented by the chemical formula (M-1d), in the general formula (M-1), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are 6-sulfolithium benzoates. Carbon in which thiazol-2-yl group, R ₁₅ and R ₁₆ are 2,6-diethyl-4-methyl-3-sulfolithium phenyl group, R ₇ is a hydrogen atom, and A ₁ is substituted with a methyl group In this embodiment, the atom A ₂ is a carbon atom.

In the compound represented by the chemical formula (M-1e), in the general formula (M-1), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are 6-sulfopotassium benzoates. A thiazol-2-yl group, R ₁₅ and R ₁₆ are 3-sulfo potassium salt-mesityl groups, R ₁₇ is a hydrogen atom, A ₁ is a carbon atom substituted with a methyl group, and A ₂ is a carbon atom It is an aspect.

In the compound represented by the chemical formula (M-1f), in the general formula (M-1), R ₁₁ is a tert-butyl group, R ₁₂ is a cyano group, R ₁₃ and R ₁₄ are 6-sulfolithium benzoates. A thiazol-2-yl group, R ₁₅ and R ₁₆ are 2,6-diethyl-4-sulfolithium phenyl groups, R ₁₇ is a hydrogen atom, and A ₁ is a carbon atom substituted with a methyl group, A ₂ Is an embodiment in which is a carbon atom.

  The blending amount of the dye (M-1) is not particularly limited. By including the dye (M-1) in the magenta ink, the fastness of a recorded matter using the magenta ink can be improved. As described above, the blending amount of the dye (M-1) is preferably in the range of 1 to 5% by weight, more preferably 1.5 to 4.5% by weight, based on the total amount of the magenta ink. is there.

  The magenta colorant may be composed of only the dye (M-1) or may further contain other dyes and pigments.

  The water and its blending amount are the same as the water and its blending amount in the yellow ink described above.

  The water-soluble organic solvent is classified into, for example, a wetting agent that prevents the ink from drying at the tip of the ink jet head and a penetrating agent that adjusts the drying speed on the recording paper surface.

Examples of the wetting agent include polyhydric alcohols. The polyhydric alcohol is not limited, and examples thereof include alkylene glycol and glycerin. The alkylene glycol is not limited, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, thiodiglycol, and hexylene glycol. The polyhydric alcohol may be used alone or in combination of two or more. The wetting agent may be composed only of the polyhydric alcohol, or may further contain another wetting agent. The amount of the polyhydric alcohol other than the wetting agent and the wetting agent is the same as the amount of the wetting agent and the wetting agent other than said polyhydric alcohol in the yellow ink described above.

  The magenta ink contains dipropylene glycol propyl ether (DPP) as the penetrant. As described above, the blending amount of the DPP is 1 to 3% by weight with respect to the total amount of the magenta ink (the condition of 1 ≦ y ≦ 3 is satisfied). The amount of the DPP is preferably 1.2 to 2.7% by weight.

  The penetrant may be composed only of the DPP, or may further contain other penetrants as long as the effects of the present invention are not impaired. The penetrant other than the DPP is the same as the penetrant in the yellow ink described above except for DPP.

As described above, the magenta ink contains an acetylene glycol surfactant. The acetylene glycol surfactant includes the surfactant represented by the general formula (1). In the general formula (1), p and q may be the same or different, and are a number satisfying p + q = 1 to 15, and preferably a number satisfying p + q = 3 to 11. R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ may be the same or different, and are each a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

  As the surfactant represented by the general formula (1), for example, a commercially available product may be used. Examples of the commercially available products include Olfin (registered trademark) E1010, Olphine (registered trademark) E1004, Surfynol (registered trademark) 440 and Surfinol (registered trademark) 465 manufactured by Nissin Chemical Industry Co., Ltd .; Examples thereof include acetylenol (registered trademark) E40 and acetylenol (registered trademark) E100 manufactured by KK.

  As described above, the amount of the surfactant represented by the general formula (1) is 0.5 to 2.5% by weight with respect to the total amount of the magenta ink (0.5 ≦ x ≦ 2.5). Meet the criteria). The amount of the surfactant represented by the general formula (1) is preferably 0.6 to 2% by weight.

  The magenta ink may contain a surfactant other than the surfactant represented by the general formula (1) as long as the effects of the present invention are not impaired. The surfactant other than the surfactant represented by the general formula (1) is not limited, and examples thereof include an anionic surfactant “EMAL (registered trademark)” series and “LATEMUL (registered trademark)” manufactured by Kao Corporation. ) ”Series,“ VENOL (registered trademark) ”series,“ NEOPELEX (registered trademark) ”series, NS SOAP, KS SOAP, OS SOAP,“ PELEX (registered trademark) ”series, etc .; manufactured by Lion Corporation Agents “LIPOLAN (registered trademark)” series, “LIPON (registered trademark)” series, “SUNNOL (registered trademark)” series, “LIPOTAC (registered trademark)” series, “ENAGICOL (registered trademark)” series, “LIPAL (registered trademark)” Trademark) ”series,“ LOTAT (registered trademark) ”series, etc .; manufactured by Kao Corporation On-surfactant “EMULGEN (registered trademark)” series, “RHEODOL (registered trademark)” series, “EMASOL (registered trademark)” series, “EXCEL (registered trademark)” series, “EMANON (registered trademark)” series, “ "AMIET (registered trademark)" series, "AMINON (registered trademark)" series, etc .; Nonionic surfactant "DOBANOX (registered trademark)" series, "LEOCOL (registered trademark)" series, "LEOX (registered trademark)" manufactured by Lion Corporation Trademark) series, “LAOL (registered trademark)” series, “LEOCON (registered trademark)” series, “LIONOL (registered trademark)” series, “CADENAX (registered trademark)” series, “LIONON (registered trademark)” series, "LEOFAT (registered trademark)" series etc. That. One type of surfactant other than the surfactant represented by the general formula (1) may be used, or two or more types may be used.

  The magenta ink may further contain a conventionally known additive as required. The additive is the same as the additive in the yellow ink described above except for the surfactant.

  The magenta ink is prepared by, for example, uniformly mixing a magenta colorant, water, a water-soluble organic solvent, and an acetylene glycol-based surfactant with other additive components as necessary using a conventionally known method, and using a filter. It can be prepared by removing the lysate.

  As described above, the magenta ink is formulated so that the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) satisfy the conditions (i) and (ii). It is excellent in ejection stability and print quality, and it is possible to prevent elution of a compound derived from a rubber member or the like in an ink jet recording apparatus into magenta ink.

In the magenta ink, the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) are further blended so as to satisfy the following condition (v).

(V) y ≧ −2x + 3 and y ≦ −2x + 6
x: blending amount (wt%) of the surfactant represented by the general formula (1) with respect to the total amount of magenta ink
y: blending amount of dipropylene glycol propyl ether with respect to the total amount of magenta ink (% by weight)

Thereby, it is possible to obtain a magenta ink that is superior in print quality.

Next, preferred specific examples of the magenta ink will be described. However, the magenta ink is not limited to this example.
(The first of magenta ink)
In the magenta ink of this example, the magenta colorant contains the following dye (M-2) in addition to the dye (M-1).
Dye (M-2): Dye (M-2a) in which the free acid is represented by formula (M-2a), C.I. I. Acid Red 52 and C.I. I. At least one dye selected from the group consisting of Acid Red 289

As described above, in the general formula (M-2a),
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 carboxyl group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
r is 0, 1 or 2;
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 aralkyl group, substituted or unsubstituted It is a substituted alicyclic group, a substituted or unsubstituted heterocyclic group, and R ₂₁ , R ₂₂ and R ₂₃ may be the same or different.

In the general formula (M-2a), 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 the same substituents as the substituents of the substituted alkyl group of the dye (M-1) represented by the general formula (M-1). .

In the general formula (M-2a), 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 general formula (M-2a), 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 general formula (M-2a), 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 general formula (M-2a), 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, Examples thereof include N-ethyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, p-carboxyphenylsulfamoyl group and the like.

In the general formula (M-2a), 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. Group and the like.

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

In the general formula (M-2a), 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 hydroxyethylsulfonyl group.

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

In the general formula (M-2a), 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 the same substituents as the substituents of the substituted alkyl group of the dye (M-1) represented by the general formula (M-1). .

In the general formula (M-2a), 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 general formula (M-2a), 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. Group and the like. Examples of the substituent of the substituted aryl group include the same substituents as the substituents of the substituted aryl group of the dye (M-1) represented by the general formula (M-1). .

In the general formula (M-2a), examples of the substituted or unsubstituted aralkyl group in R ₂₁ , R ₂₂ and R ₂₃ include a benzyl group, 1-carboxy-2-phenyl-ethyl group, 1-carboxy-2 -Hydroxyphenylethyl group, 4-carboxybenzyl group and the like.

In the general formula (M-2a), 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 general formula (M-2a), 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-tetra Examples thereof include a methylpiperidinyl group. Examples of the substituent of the substituted heterocyclic group include the same substituents as those exemplified as the substituent of the substituted heterocyclic group of the dye (M-1) represented by the general formula (M-1). can give.

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

In the general formula (M-2a), 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 number of 1 to 9 carbon atoms. 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 sulfonic acid ester group, and a carboxylic acid ester group. The groups may be the same or different.

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

  The dye (M-2a) preferably has a total of 6 or less, preferably 5 or less, particularly preferably 4 or less sulfonic acid groups and carboxyl groups or salts thereof in the structure. The dye (M-2a) may be used in the free acid form, but may be used as it is when obtained in the salt form at the time of manufacture, or may be converted into a desired salt form. Good. In addition, the dye (M-2a) may have a part of an acid group in a salt form, and a salt type dye and a free acid type dye may be mixed. Examples of such salt forms include salts of alkali metals such as Na, Li and K, ammonium salts which may be substituted with alkyl groups or hydroxyalkyl groups, and organic amine salts. 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 preferred embodiment of the dye (M-2a), for example, in the general formula (M-2a), r is 0, and R ₁₈ is a carboxyl group, a carbamoyl group, a trifluoromethyl group, a sulfamoyl group, R ₁₉ and R ₂₀ are a hydrogen atom, R ₂₁ is a phenyl group or a carboxyalkyl group which may be substituted with a carboxyl group or a sulfamoyl group, R ₂₂ is a hydrogen atom, and R ₂₃ is a hydrogen atom or an alkyl group The aspect which is is mention | raise | lifted.

  Specific preferred specific examples of the dye (M-2a) include compounds represented by the following chemical formulas (M-2a-1) to (M-2a-5).

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

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

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

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

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

  C. I. Acid Red 52 is, for example, a dye represented by the following chemical formula (M-2b).

  C. I. Acid Red 289 is, for example, a dye represented by the following chemical formula (M-2c).

  In the magenta ink of this example, the blending amount of the dye (M-2) is not particularly limited. By including the dye (M-2) in the magenta ink, it is possible to obtain a magenta ink having better color developability. The blending amount of the dye (M-2) is, for example, 0.1 to 2.1% by weight, preferably 0.3 to 1.4% by weight, based on the total amount of the magenta ink.

  The weight ratio of the dye (M-1) and the dye (M-2) in the magenta ink of this example is dye (M-1): dye (M-2) = 70: 30 to 90:10. It is preferable.

  In the magenta ink of this example, the total amount of the dye (M-1) and the dye (M-2) is not particularly limited, but is 1.1 to 7.1% by weight with respect to the total amount of the magenta ink. And more preferably 2 to 5% by weight.

The composition of the magenta ink of this example other than these is the same as that of the magenta ink.

(Cyan ink)
Next, the cyan ink will be described. As described above, the cyan ink includes a cyan colorant, water, and a water-soluble organic solvent. The cyan colorant includes the dye (C-1) and the dye (C-2).

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

As described above, in the general formula (C-1),
Pc (Cu) is a copper phthalocyanine nucleus represented by the general 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 , R ₃₃ and R ₃₄ are present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc), and R _a is substituted or An unsubstituted alkyl group, R _b is a hydrogen atom, a substituted or unsubstituted alkyl group, R _c is a substituted or unsubstituted alkyl group,
k is an integer satisfying 0 <k <8, l is an integer satisfying 0 <l <8, m is an integer satisfying 0 ≦ m <8, and n is 0 ≦ n <8 And k, l, m and n are integers satisfying 4 ≦ k + 1 + m + n ≦ 8.

  In the general formula (C-1), 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 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 general formula (C-1), 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 atoms and bromine atoms; phenyl groups, 4-tert-butylphenyl groups Aryl groups such as 2,4-di-tert-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 -Aryloxy groups such as butylphenoxy group, 3-nitrophenoxy group, 3-tert-butoxycarbamoylphenoxy group, 3-methoxycarbamoyl group; acetamide group, benzamide group, 4- (3-tert-butyl-4-hydroxyphenoxy) ) Acylamino group such as butanamide group; Alkylamino groups such as phenyl group, butylamino group, diethylamino group and methylbutylamino group; anilino groups such as phenylamino group and 2-chloroanilino group; phenylureido group, methylureido group, N, N-dibutylureido group, etc. Ureido group; sulfamoylamino group such as N, N-dipropylsulfamoylamino group; alkylthio group such as methylthio group, octylthio group and 2-phenoxyethylthio group; phenylthio group, 2-butoxy-5-tert-octyl Arylthio groups such as phenylthio group and 2-carboxyphenylthio group; alkoxycarbonylamino groups such as methoxycarbonylamino group; sulfonamide groups such as methanesulfonamide group, benzenesulfonamide group and p-toluenesulfonamide; N-ethyl Carbamoyl group, N, N A carbamoyl group such as dibutylcarbamoyl group; a sulfamoyl group such as N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N-phenylsulfamoyl group; methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group Sulfonyl groups such as toluenesulfonyl group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; heterocyclic oxy groups such as 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group; phenylazo group, 4 -Azo groups such as methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo; acyloxy groups such as acetoxy group; N-methylcarbamoyloxy group, N-phenylcarbamoyloxy Carba such as group Silyloxy groups such as trimethylsilyloxy group and dibutylmethylsilyloxy group; aryloxycarbonylamino groups such as phenoxycarbonylamino group; imide groups such as N-succinimide and N-phthalimide; 2-benzothiazolylthio group, 2 , 4-diphenoxy-1,3,5-triazole-6-thio group, heterocyclic thio group such as 2-pyridylthio group; sulfinyl group such as 3-phenoxypropylsulfinyl group; phenoxyphosphonyl group, octyloxyphosphonyl group Phosphonyl group such as phenylphosphonyl group; aryloxycarbonyl group such as phenoxycarbonyl group; acyl group such as acetyl group, 3-phenylpropanoyl group and benzoyl group; carboxyl group, sulfo group, phosphono group, quaternary ammonium group Ionicity such as Aqueous group, and the like. 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, are branched from the viewpoint of improving dye solubility and ink stability. Those having a chain are preferred, and those having an asymmetric carbon are particularly preferred.

As a preferable aspect of the dye (C-1), for example, in the general formula (C-1), R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each —SO _{2 Ra} , and R ₃₁ not that all of _{R a} with _{R 32, R 33} and _{R 34} are each is 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 preferable embodiment of the dye (C-1), for example, in the general formula (C-1), k is an integer satisfying 0 <k <4, and l satisfies 0 <l <4. M is an integer satisfying 0 ≦ m <4, n is an integer satisfying 0 ≦ n <4, and k, l, m, and n are integers satisfying k + 1 + m + n = 4 It is a certain aspect.

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

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

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

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

In the compound represented by the chemical formula (C-1d), in the general formula (C-1), R ₃₁ is a lithium sulfonatopropylsulfonyl group, and R ₃₂ is N- (2-hydroxypropyl) sulfamoylpropylsulfonyl. In this embodiment, the 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 chemical formula (C-1e), in the general formula (C-1), R ₃₁ is a lithium sulfonatopropylsulfonyl group, R ₃₂ is a lithium carboxylatopropylsulfonyl group, and R ₃₃ is N- ( In this embodiment, 2-hydroxypropyl) sulfamoylpropylsulfonyl group, R ₃₄ is N- (2-hydroxyisopropyl) sulfamoylpropylsulfonyl group, and k, l, m and n are all 1.

  The compounding amount of the dye (C-1) is not particularly limited. By including the dye (C-1) in the cyan ink, the fastness of the recorded matter using the cyan ink can be improved. As described above, the blending amount of the dye (C-1) is preferably in the range of 1 to 5% by weight, more preferably 1.5 to 4% by weight, based on the total amount of the cyan ink.

  As described above, the dye (C-2) is a dye represented by the general formula (C-2).

In the general formula (C-2),
Pc (Cu) is a copper phthalocyanine nucleus represented by the general formula (Pc),
s is an integer that satisfies 0 <s <4, t is an integer that satisfies 0 ≦ t <4, and s and t are integers that satisfy 2 ≦ s + t ≦ 5.
The SO ₃ M ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc),
At t ≠ 0, the SO ₂ NH ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc);
M ₂ is a lithium ion, a sodium ion, a potassium ion or an ammonium ion.

  Preferable specific examples of the dye (C-2) include compounds represented by the following chemical formulas (C-2a) to (C-2d) and C.I. I. Direct Blue 86 is listed.

In the compound represented by the chemical formula (C-2a), in the general formula (C-2), M ₂ is a sodium ion, s is 1, t is 3, one SO ₃ Na group and 3 One SO ₂ NH ₂ group is present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc).

In the compound represented by the chemical formula (C-2b), in the general formula (C-2), M ₂ is a sodium ion, s and t are both 2, two SO ₃ Na groups, and two In this embodiment, SO ₂ NH ₂ groups are present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc).

In the compound represented by the chemical formula (C-2c), in the general formula (C-2), M ₂ is a sodium ion, s is 3, t is 1, 3 SO ₃ Na groups and 1 One SO ₂ NH ₂ group is present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc).

In the compound represented by the chemical formula (C-2d), in the general formula (C-2), M ₂ is an ammonium ion, s is 1, t is 3, and one SO ₃ NH ₄ group and In this embodiment, three SO ₂ NH ₂ groups are present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc).

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

In the dye represented by the structural formula (C-2e), in the general formula (C-2), M ₂ is a sodium ion, s is 2, t is 0, and two SO ₃ Na groups are , Respectively, are present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc).

  The compounding amount of the dye (C-2) is not particularly limited. By including the dye (C-2) in the cyan ink, the color developability can be improved. The blending amount of the dye (C-2) is, for example, 0.1 to 2.1% by weight, preferably 0.2 to 1.2% by weight, based on the total amount of the cyan ink.

As described above, the weight ratio of the dye (C-1) to the dye (C-2) in the cyan ink is as follows: Dye (C-1): Dye (C-2) = 70: 30 to 95: 5 der Ru.

  The total blending amount of the dye (C-1) and the dye (C-2) is not particularly limited, but is preferably 1.1 to 7.1% by weight based on the total amount of the cyan ink. Preferably, it is 2 to 5% by weight.

  The cyan colorant may be composed only of the dye (C-1) and (C-2), or may further contain other dyes and pigments.

  The water and its blending amount are the same as the water and its blending amount in the yellow ink described above.

The wetting agent and its blending amount are the same as the wetting agent and its blending amount in the magenta ink described above. The penetrant and the blending amount thereof are the same as the penetrant and the blending amount thereof in the yellow ink described above.

  The cyan ink may further contain a conventionally known additive as required. The additive is the same as the additive in the aforementioned yellow ink.

  The cyan ink is prepared by, for example, uniformly mixing a cyan colorant, water, a water-soluble organic solvent, and, if necessary, other additive components by a conventionally known method, and removing insoluble matters with a filter. Can be prepared.

In the ink set for ink jet recording of the present invention, examples of preferable combinations of the inks of the respective colors include sets 1 to 6 shown in Table 1. However, these combinations are merely examples, and the ink set for inkjet recording of the present invention is not limited to this.

(Table 1)
Yellow ink Magenta ink Cyan ink
Set 1 Yellow ink Magenta ink Cyan ink set 2 Yellow ink First magenta ink Cyan ink set 3 First yellow ink Magenta ink Cyan ink set 4 First yellow ink First magenta ink Cyan ink set 5 Second yellow Ink Magenta ink Cyan ink set 6 Second yellow ink First magenta ink Cyan ink

  The ink set for ink-jet recording of the present invention can support full-color recording by including the three color inks. The ink set of the present invention may be composed of only the three color inks, or may further include other color inks. Examples of the other color ink include black ink, red ink, green ink, blue ink, and light ink with low dye concentration (light yellow ink, light magenta ink, light cyan ink, light black ink, light red ink, light ink). Green ink, light blue ink, etc.). It is particularly preferable that the ink set of the present invention contains a black ink because full color recording can be more suitably supported.

  As described above, the ink cartridge of the present invention is an ink cartridge having storage portions for yellow ink, magenta ink, and cyan ink, and the yellow ink, magenta ink, and cyan ink are the ink jet ink of the present invention. These are the yellow ink, magenta ink, and cyan ink of the recording ink set. The ink cartridge of the present invention may further include a storage portion for the other color ink.

  The ink cartridge of the present invention is preferably an ink cartridge assembly in which a plurality of ink cartridges each having an ink storage portion for one color are collected. However, the present invention is not limited to this. The ink cartridge of the present invention may be an integrated ink cartridge whose interior is partitioned so as to form an ink storage portion for each color. As the main body of the ink cartridge of the present invention, for example, a conventionally known one can be used.

  Next, the ink jet recording apparatus of the present invention will be described. The ink jet recording apparatus of the present invention includes the ink cartridge of the present invention. Except for this, the configuration of the ink jet recording apparatus of the present invention may be the same as that of a conventionally known ink jet recording apparatus, for example.

  FIG. 1 shows the configuration of an example of the ink jet recording apparatus of the present invention. As shown in the figure, the ink jet recording apparatus 1 includes four ink cartridges 2, an ink jet head 3, a head unit 4, a carriage 5, a drive unit 6, a platen roller 7, and a purge device 8. Including as a member.

  The four ink cartridges 2 contain one color each of four colors of yellow, magenta, cyan, and black. The four color inks are the yellow ink, magenta ink, cyan ink and black ink of the ink set of the present invention. The ink jet head 3 performs printing on a recording material P such as recording paper. The head unit 4 includes the inkjet head 3. The four ink cartridges 2 and the head unit 4 are mounted on the carriage 5. The drive unit 6 reciprocates the carriage 5 in a linear direction. The platen roller 7 extends in the reciprocating direction of the carriage 5 and is disposed to face the ink jet head 3.

  The drive unit 6 includes a carriage shaft 9, a guide plate 10, two pulleys 11 and 12, and an endless belt 13. The carriage shaft 9 is disposed at the lower end of the carriage 5 and extends in parallel with the platen roller 7. The guide plate 10 is disposed at the upper end of the carriage unit 5 and extends in parallel with the carriage shaft 9. The two pulleys 11 and 12 are disposed between the carriage shaft 9 and the guide plate 10 at both ends of the carriage shaft 9. The endless belt 13 is stretched between the two pulleys 11 and 12.

  In the ink jet recording apparatus 1, when the pulley 11 is rotated forward and backward by driving the carriage motor 101, the carriage 5 joined to the endless belt 13 is moved along with the forward and reverse rotation of the pulley 11. Along the carriage shaft 9 and the guide plate 10, it reciprocates in a linear direction.

  The recording material P is fed from a paper feed cassette (not shown) provided on the side or lower side of the ink jet recording apparatus 1. The recording material P is introduced between the inkjet head 3 and the platen roller 7. Then, predetermined printing is performed on the recording material P by the ink ejected from the inkjet head 3. Thereafter, the recording material P is discharged from the ink jet recording apparatus 1. In FIG. 1, the paper feed mechanism and paper discharge mechanism for the recording material P are not shown.

  The purge device 8 is provided on the side of the platen roller 7 so as to face the inkjet head 3 when the head unit 4 is at a reset position (in this example, the upper portion of the purge device 8). Has been placed. The purge device 8 includes a purge cap 14, a pump 15 and a cam 16, and an ink storage unit 17. The purge cap 14 covers a plurality of nozzles (not shown) of the inkjet head 3 when the head unit 4 is in the reset position. The pump 15 sucks out defective ink containing bubbles and the like accumulated in the ink jet head 3 by driving the cam 16. Thereby, recovery of the inkjet head is achieved. The sucked defective ink is stored in the ink storage unit 17.

  A wiper member 20 is disposed adjacent to the purge device 8 at a position 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 forming surface of the inkjet head 3 as the carriage 5 moves. In FIG. 1, a cap 18 covers a plurality of nozzles of the inkjet head 3 that is returned to the reset position when printing is completed in order to prevent ink from drying.

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

  Next, examples of the present invention will be described together with comparative examples. The present invention is not limited or restricted by the following examples and comparative examples.

[Preparation of yellow ink]
The ink composition components (Table 2) were mixed uniformly. Thereafter, the resultant mixture by filtration using Toyo Filter Paper Co., Ltd. hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size 0.2 [mu] m), a yellow ink Y1～Y 5 and Y 6 It was obtained c~Y 9 c. In Table 2, dyes (Y-1a) to (Y-1e) are compounds represented by the chemical formulas (Y-1a) to (Y-1e), respectively.

[Preparation of magenta ink]
The ink composition components (Table 3) were mixed uniformly. Thereafter, the resultant mixture by filtration using Toyo Filter Paper Co., Ltd. hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore size 0.2 [mu] m), magenta ink M1 to M 4 and M 10 It was obtained c~M 18 c. In Table 3, dyes (M-1a) to (M-1f) are compounds represented by the chemical formulas (M-1a) to (M-1f), respectively, and dyes (M-2a-1) ) To (M-2a-5) are compounds represented by the chemical formulas (M-2a-1) to (M-2a-5), respectively.

[Preparation of cyan ink]
The ink composition components (Table 4) were mixed uniformly. Thereafter, the obtained mixture is filtered using a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore diameter 0.2 μm) manufactured by Toyo Roshi Kaisha, Ltd., so that cyan inks C1 to C6 and C7c to C11c are obtained. Got. In Table 4, dyes (C-1a) to (C-1e) are compounds represented by the chemical formulas (C-1a) to (C-1e), respectively, and dyes (C-2a) to (C-2a) (C-2d) is a compound represented by the chemical formulas (C-2a) to (C-2d), respectively.

  Table 2 shows the composition of each yellow ink. Table 3 shows the composition of each magenta ink. Further, Table 4 shows the composition of each cyan ink.

[Examples 1-5, Comparative Examples 1-7, and Reference Examples 1-2 ]
[Configuration of ink set for inkjet recording]
As shown in Tables 5 and 6, an ink set for inkjet recording was configured by combining yellow ink, magenta ink, and cyan ink.

For the ink sets of each example , each comparative example, and each reference example , (a) storage stability evaluation, (b) ozone resistance evaluation, (c) light resistance evaluation, (d) color development evaluation, (e) printing Quality evaluation (bleeding), (f) injection stability evaluation, (g) rubber precipitation evaluation, and (h) comprehensive evaluation were performed by the following methods. Samples for (b) ozone resistance evaluation and (c) light resistance evaluation were prepared as follows.

The yellow ink, the magenta ink, and the cyan ink constituting the ink set of each example , each comparative example, and each reference example are filled in the ink cartridge, and the ink cartridge is an ink jet printer manufactured by Brother Industries, Ltd. The digital multifunction device DCP-330C was mounted. Next, a single color gradation sample of the ink was printed on photographic glossy paper BP61GLA manufactured by Brother Industries, Ltd. to obtain each single color patch with an initial OD value of 1.0. The OD value was measured with a spectrocolorimeter Spectrolino (light source: D ₆₅ ; field of view: 2 °; status A) manufactured by Gretag Macbeth.

(A) Storage Stability Evaluation The absorbance at the maximum absorption peak wavelength of a diluted solution obtained by diluting each ink constituting the ink set of each Example , each Comparative Example and each Reference Example 1600 times with pure water was calculated using Shimadzu Corporation. It measured using the ultraviolet visible near-infrared spectrophotometer UV3600 made from a manufacturing company. A measurement cell having a cell length of 10 mm was used for measuring the absorbance. Subsequently, the ink was separately put in a sealed container and stored in an environment of a temperature of 60 ° C. for 2 weeks. Next, the absorbance of the diluted solution obtained by diluting the ink after the storage with pure water 1600 times was measured in the same manner as before the storage. Next, the absorbance decrease rate (%) was determined by the following formula (I), and the storage stability as an ink set was evaluated according to the following evaluation criteria. In addition, the smaller the absorbance decrease rate, the better the storage stability.

Absorbance decrease rate (%) = {(XY) / X} × 100 (I)
X: Absorbance before storage Y: Absorbance after storage

Storage stability evaluation criteria AA: Ink absorbance decrease rate of ink is less than 5% A: Absorption decrease rate of at least one color ink is 5% or more and less than 10%, and remaining ink absorbance decrease rate is less than 5% C : Absorption decrease rate of at least one color ink is 10% or more

(B) Ozone resistance evaluation Using the ozone weather meter OMS-H manufactured by Suga Test Instruments Co., Ltd., each of the monochromatic patches was applied under the conditions of an ozone concentration of 2 ppm, a tank temperature of 24 ° C, and a tank relative humidity of 60%. Left for 80 hours. The OD value of each single color patch after the standing was measured. The OD value reduction rate (%) was determined by the following formula (II), and the ozone resistance was evaluated according to the following evaluation criteria. Note that the smaller the OD value reduction rate, the less the deterioration of image quality and the better the ozone resistance.

OD value reduction rate (%) = {(XY) / X} × 100 (II)
X: 1.0 (initial OD value)
Y: OD value after standing

Ozone resistance evaluation standard A: OD value reduction rate of ink is less than 30%, and maximum difference of OD value reduction rate between inks is less than 20% C: OD value reduction of ink of at least one color The rate is 30% or more, or the maximum difference in OD value reduction rate between any of the inks is 20% or more

(C) Light resistance evaluation Using the high energy xenon weather meter SC750-WN manufactured by Suga Test Instruments Co., Ltd., each of the above-mentioned single color patches was applied under the conditions of a tank temperature of 25 ° C., a tank relative humidity of 50%, and an illuminance of 93 klx. Xenon lamp light was irradiated for 200 hours. The OD value of each single color patch after the irradiation was measured. The OD value reduction rate (%) was determined by the following formula (III), 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 reduction rate (%) = {(XY) / X} × 100 (III)
X: 1.0 (initial OD value)
Y: OD value after irradiation

Light fastness evaluation criteria A: OD value reduction rate of ink is less than 30%, and maximum difference of OD value reduction rate between inks is less than 20% C: OD value reduction rate of ink of at least one color Is 30% or more, or the maximum difference in the OD value reduction rate between any of the inks is 20% or more

(D) Evaluation of coloring property Each ink cartridge is filled with yellow ink, magenta ink, and cyan ink constituting the ink set of each example , each comparative example, and each reference example , and the ink cartridge is connected to Brother Industries, Ltd. It was mounted on a digital multifunction printer DCP-330C equipped with an inkjet printer. Next, a natural image sample (JIS SCID No. 2) was printed on photographic glossy paper BP60GLA manufactured by Brother Industries. This natural image sample was visually observed, and whether or not a single color or a combination of colors was sufficiently expressed was evaluated according to the following evaluation criteria.

Criteria for evaluation of color development AA: A single color and a combination of each color can be sufficiently expressed A: A single color can be expressed sufficiently C: A single color and a combination of each color cannot be expressed sufficiently

(E) Print quality evaluation (bleeding)
Using the digital multifunction printer DCP-330C equipped with an inkjet printer manufactured by Brother Industries, Ltd., the background is the ink set of each example , each comparative example, and each reference example on the office paper W manufactured by Fujitsu Coalco. The yellow ink, the magenta ink, the cyan ink, and the evaluation sample to be printed were black inks filled in an ink cartridge LC10BK manufactured by Brother Industries, Ltd., and printed. Rag at the boundary between the yellow ink, magenta ink, cyan ink and the black ink was measured by a method according to ISO 13660. Here, “Rag” is the ruggedness of the line defined by ISO 13660, and the “rugget line” indicates a state of undulation with respect to an ideal line edge that should be smooth and straight. The obtained Rag was evaluated according to the following evaluation criteria.

Print quality evaluation (bleeding) criteria A: In the ink, the line rag is less than 18 C: In any ink, the line rag is 18 or more

(F) Evaluation of ejection stability For each of the yellow ink, magenta ink, and cyan ink constituting the ink set of each example , each comparative example, and each reference example, a digital multifunction device DCP equipped with an inkjet printer manufactured by Brother Industries, Ltd. Using −330C, solid printing with a resolution of 600 dpi × 600 dpi and a coverage rate of 100% was performed on office paper W manufactured by Fujitsu Cower Co., Ltd., and 20 evaluation samples were produced. The evaluation samples were visually observed for the presence of printing defects (non-ejection and ejection disturbance) and evaluated according to the following evaluation criteria.

Criteria for evaluating jetting stability A: No printing failure was observed in any ink C: Printing failure was observed in any ink

(G) Evaluation of rubber deposition property A rubber piece is added to the ink under the condition that the contact area per 1 g of ink is 30 mm ² for each of the yellow ink, magenta ink, and cyan ink constituting the ink set of each Example and each Comparative Example. (Ethylene propylene rubber (EPDM); rubber hardness (measured by old JIS K 6301 type A) 40 °) was immersed and stored for 1 week in an environment of 70 ° C. After the storage, the rubber piece was taken out from the ink, and then the ink was filtered with a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore diameter: 0.2 μm; diameter: 15 mm) manufactured by Toyo Roshi Kaisha, Ltd. The time required for filtration was measured. As a control, the ink before storage was filtered under the same conditions as described above, and the time required for filtration was measured. Next, the increase rate of filtration time was calculated | required by following formula (IV), and rubber | gum precipitation nature was evaluated in accordance with the following evaluation criteria.

Increase rate of filtration time = Y / X (IV)
X: Filtration time before storage Y: Filtration time after storage

(G) Rubber precipitation evaluation For each of the yellow ink, magenta ink, and cyan ink constituting the ink set of each example , each comparative example, and each reference example , the contact area per 1 g of ink is 30 mm ^2. A rubber piece (ethylene propylene rubber (EPDM); rubber hardness (measured by old JIS K 6301 A type) 40 °) was immersed in the ink, and stored in an environment at a temperature of 70 ° C. for 1 week. After the storage, the rubber piece was taken out from the ink, and then the ink was filtered with a hydrophilic polytetrafluoroethylene (PTFE) type membrane filter (pore diameter: 0.2 μm; diameter: 15 mm) manufactured by Toyo Roshi Kaisha, Ltd. The time required for filtration was measured. As a control, the ink before storage was filtered under the same conditions as described above, and the time required for filtration was measured. Next, the increase rate of filtration time was calculated | required by following formula (IV), and rubber | gum precipitation nature was evaluated in accordance with the following evaluation criteria.

(H) Comprehensive evaluation For each ink set, comprehensive evaluation was performed according to the following evaluation criteria from the results of (a) to (g).

Overall evaluation criteria G: C was not found in any of the evaluation results NG: C was found in any of the evaluation results

Table 5 shows the configuration and evaluation results of the ink set of each example. Table 6 shows the configurations and evaluation results of the ink sets of each comparative example and each reference example .

As shown in Table 5, the ink sets of Examples 1 to 5 are storage stability evaluation, ozone resistance evaluation, light resistance evaluation, color development evaluation, print quality evaluation (bleeding), jetting stability evaluation, and rubber precipitation. All results of the evaluation were good. As shown in Table 5 and Table 6, in the ink sets of Examples 1 to 5, the storage stability evaluation result was “AA”, whereas the inks of Comparative Example 7 and Reference Examples 1 and 2 were used. In the set, the result of storage stability evaluation was “A”.

  On the other hand, as shown in Table 6, the ink set of Comparative Example 1 has poor results of ozone resistance evaluation and light resistance evaluation because the yellow ink does not contain the dye (Y-1). Since the blending amount was small, the result of printing quality evaluation (bleeding) was inferior, and since the cyan ink did not contain the dye (C-2), the result of color development evaluation was inferior. Further, the difference in the OD value reduction rate in the ozone resistance evaluation and the light resistance evaluation between the yellow ink and the magenta ink and between the yellow ink and the cyan ink was large, and the color balance was poor.

  In addition, the ink set of Comparative Example 2 is inferior in the results of ozone resistance evaluation and light resistance evaluation because the yellow ink does not contain the dye (Y-1), and is stable in jetting because the blending amount of magenta ink DPP is large. The results of the property evaluation were inferior, and since the cyan ink did not contain the dye (C-1), the results of the ozone resistance evaluation were inferior. Furthermore, the difference in the OD value decrease rate in the ozone resistance evaluation and the light resistance evaluation between the yellow ink and the magenta ink and between the yellow ink and the cyan ink is also large, and the OD value decrease rate in the ozone resistance evaluation between the magenta ink and the cyan ink. The difference in color was large and the color balance was bad.

  In addition, the ink set of Comparative Example 3 has a poor print quality evaluation (bleeding) result because the amount of the surfactant represented by the general formula (1) of the magenta ink is small, and the cyan ink is a dye (C -1) was not included, the results of ozone resistance evaluation were inferior. Furthermore, the difference in the OD value reduction rate in the ozone resistance evaluation between the yellow ink and the cyan ink and between the magenta ink and the cyan ink was large, and the color balance was poor.

  Further, the ink set of Comparative Example 4 has a poor rubber precipitation evaluation result due to the large amount of the surfactant represented by the general formula (1) of the magenta ink, and the cyan ink is a dye (C-1 ) Was not included, the results of ozone resistance evaluation were inferior. Furthermore, the difference in the OD value reduction rate in the ozone resistance evaluation between the yellow ink and the cyan ink and between the magenta ink and the cyan ink was large, and the color balance was poor.

  Further, in the ink set of Comparative Example 5, the magenta ink does not contain DPP, and dipropylene glycol methyl ether is blended in place of DPP, so the result of printing quality evaluation (bleeding) is inferior, and the cyan ink is a dye. Since (C-1) and dye (C-2) were not included, the results of ozone resistance evaluation and light resistance evaluation were inferior. Furthermore, the difference in the OD value reduction rate in the ozone resistance evaluation between the yellow ink and the cyan ink and between the magenta ink and the cyan ink was large, and the color balance was poor.

  Further, in the ink set of Comparative Example 6, since the magenta ink did not contain DPP and dipropylene glycol butyl ether was blended instead of DPP, the result of rubber deposition evaluation was inferior.

Further, in the ink set of Comparative Example 7 , since the magenta ink does not contain the dye (M-1) and the dye (M-2), the results of ozone resistance evaluation, light resistance evaluation, and color development evaluation are inferior. Since the ink did not contain the dye (C-2), the color development evaluation results were inferior. Further, the difference in the OD value reduction rate in the ozone resistance evaluation and the light resistance evaluation between the yellow ink and the magenta ink and between the magenta ink and the cyan ink was large, and the color balance was poor.

  As described above, the ink set of the present invention is excellent in fastness such as light resistance and ozone resistance of recorded matter, and has little change in the color balance of an image even if the color is faded. The use of the ink set of the present invention is not limited and can be widely applied to various ink jet recordings.

FIG. 1 is a schematic perspective view showing an example of the configuration of the ink jet recording apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inkjet recording device 2 Ink cartridge 3 Inkjet head 4 Head unit 5 Carriage 6 Drive unit 7 Platen roller 8 Purge device 9 Carriage shaft 10 Guide plate

Claims (14)

An ink set for inkjet recording containing yellow ink, magenta ink and cyan ink,
The yellow ink contains a yellow colorant, water and a water-soluble organic solvent, the yellow colorant is a dye (Y-1) represented by the following general formula (Y-1), and the water-soluble organic solvent is multivalent. Including alcohol;
The magenta ink contains a magenta colorant, water, a water-soluble organic solvent, and an acetylene glycol surfactant, and the magenta colorant is a dye (M-1) represented by the following general formula (M-1), The water-soluble organic solvent contains dipropylene glycol propyl ether, the acetylene glycol surfactant contains a surfactant represented by the following general formula (1), and the dipropylene glycol propyl ether and the general formula (1) Are blended so as to satisfy the following conditions (i) and (ii) respectively:

(I) 0.5 ≦ x ≦ 2.5
(Ii) 1 ≦ y ≦ 3
x: blending amount (wt%) of the surfactant represented by the general formula (1) with respect to the total amount of magenta ink
y: blending amount of dipropylene glycol propyl ether with respect to the total amount of magenta ink (% by weight)

The cyan ink contains a cyan colorant, water, and a water-soluble organic solvent, and the cyan colorant is represented by the following general formula (C-1) (C-1) and the following general formula (C-2). A dye (C-2) represented by
In the yellow ink, the polyhydric alcohol may or may not contain glycerin, and the blending ratio of the dye (Y-1) and glycerin is set to satisfy the following condition (iv ′):

(Iv ′) 0 ≦ Y2 ≦ 3.5X
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (% by weight)

In the magenta ink, the dipropylene glycol propyl ether and the surfactant represented by the general formula (1) are further blended so as to satisfy the following condition (v):

(V) y ≧ −2x + 3 and y ≦ −2x + 6
x: blending amount (wt%) of the surfactant represented by the general formula (1) with respect to the total amount of magenta ink
y: blending amount of dipropylene glycol propyl ether with respect to the total amount of magenta ink (% by weight)

The weight ratio of the dye (C-1) to the dye (C-2) in the cyan ink is dye (C-1): dye (C-2) = 70: 30 to 95: 5. Ink set for ink jet recording characterized.

In the general 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, substitution or unsubstituted aryl group, a substituted or unsubstituted A heterocyclic 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 general formula (M-1),
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 nitrogen atom.

In the general formula (C-1),
Pc (Cu) is a copper phthalocyanine nucleus represented by the following general 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 , R ₃₃ and R ₃₄ are present in each of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc), and R _a is substituted or An unsubstituted alkyl group, R _b is a hydrogen atom, a substituted or unsubstituted alkyl group, R _c is a substituted or unsubstituted alkyl group,
k is an integer satisfying 1 ≦ k ≦ 7 , l is an integer satisfying 1 ≦ l ≦ 7 , m is an integer satisfying 0 ≦ m ≦ 6 , and n is 0 ≦ n ≦ 6 And k, l, m and n are integers satisfying 4 ≦ k + 1 + m + n ≦ 8.

In the general formula (C-2),
Pc (Cu) is a copper phthalocyanine nucleus represented by the general formula (Pc),
s is an integer that satisfies 0 <s <4, t is an integer that satisfies 0 ≦ t <4, and s and t are integers that satisfy 2 ≦ s + t ≦ 5.
The SO ₃ M ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc),
At t ≠ 0, the SO ₂ NH ₂ group is present in any of the four benzene rings A, B, C and D in the copper phthalocyanine nucleus represented by the general formula (Pc);
M ₂ is lithium, sodium, potassium or NH ₄ .

In the general formula (1), p and q may be the same or different, and are numbers satisfying p + q = 1 to 15,
R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ may be the same or different and are each a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms . 2. The ink set for ink jet recording according to claim 1, wherein in the yellow ink, the blending ratio of the dye (Y-1) and glycerin is set so as to satisfy the following condition (iv ″).

(Iv ″) 3.5X−5 ≦ Y2
X: blending ratio (% by weight) of the dye (Y-1) with respect to the total amount of yellow ink
Y2: Blending ratio of glycerin with respect to the total amount of yellow ink (wt%) 3. The ink set for ink jet recording according to claim 1, wherein the amount of the dye (Y-1) is 1 to 5% by weight based on the total amount of the yellow ink. The yellow colorant further contains the following dye (Y-2), and the weight ratio of the dye (Y-1) to the dye (Y-2) in the yellow ink is dye (Y-1): Dye (Y-2) = 70: 30-90: 10 The ink set for inkjet recording as described in any one of Claims 1-3.
Dye (Y-2): C.I. I. Direct Yellow 86 and C.I. I. At least one of Direct Yellow 132 The ink set for inkjet recording according to claim 4, wherein the total amount of the dye (Y-1) and the dye (Y-2) is 1.1 to 7.1% by weight with respect to the total amount of the yellow ink. . The ink set for inkjet recording according to any one of claims 1 to 5, wherein a blending amount of the dye (M-1) is 1 to 5% by weight with respect to a total amount of the magenta ink. The magenta colorant further contains the following dye (M-2), and the weight ratio of the dye (M-1) and the dye (M-2) in the magenta ink is a dye (M-1): It is dye (M-2) = 70: 30-90: 10, The ink set for inkjet recording as described in any one of Claims 1-6.
Dye (M-2): Dye (M-2a) whose free acid is represented by the following general formula (M-2a), C.I. I. Acid Red 52 and C.I. I. At least one dye selected from the group consisting of Acid Red 289

In the general formula (M-2a),
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 carboxyl group, a carboxylic acid ester group, R ₁₈ , R ₁₉ and R ₂₀ may be the same or different,
r is 0, 1 or 2;
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, substitution or unsubstituted alicyclic group, a substituted Or it is an unsubstituted heterocyclic group, R <_21> , R <_22> and R < ₂₃ > may be the same or different. The ink set for ink-jet recording according to claim 7, wherein the total amount of the dye (M-1) and the dye (M-2) is 1.1 to 7.1% by weight with respect to the total amount of the magenta ink. . The ink set for inkjet recording according to any one of claims 1 to 8, wherein a blending amount of the dye (C-1) is 1 to 5% by weight with respect to the total amount of the cyan ink. The total blending amount of the dye (C-1) and the dye (C-2) is 1.1 to 7.1% by weight with respect to the total amount of the cyan ink. The ink set for inkjet recording as described in 2. The dye (Y-1) represented by the general formula (Y-1) is a compound represented by the chemical formula (Y-1a), a compound represented by the chemical formula (Y-1b), or a chemical formula (Y-1c). At least one compound selected from the group consisting of a compound represented by formula (Y-1d) and a compound represented by formula (Y-1e):
The dye (M-1) represented by the general formula (M-1) is a compound represented by the chemical formula (M-1a), a compound represented by the chemical formula (M-1b), or a chemical formula (M-1c). At least one compound selected from the group consisting of a compound represented by formula (M-1d), a compound represented by formula (M-1e), and a compound represented by formula (M-1f) And
The dye (C-1) represented by the general formula (C-1) is a compound represented by the chemical formula (C-1a), a compound represented by the chemical formula (C-1b), or a chemical formula (C-1c). At least one compound selected from the group consisting of a compound represented by formula (C-1d) and a compound represented by formula (C-1e):
The dye (C-2) represented by the general formula (C-2) is a compound represented by the chemical formula (C-2a), a compound represented by the chemical formula (C-2b), and a chemical formula (C-2c). A compound represented by formula (C-2d) and C.I. I. The ink set for inkjet recording according to any one of claims 1 to 10, wherein the ink set is at least one compound selected from the group consisting of direct blue 86.

The ink cartridge for ink jet recording according to any one of claims 1 to 11, wherein the ink cartridge has storage portions for yellow ink, magenta ink, and cyan ink, and the yellow ink, magenta ink, and cyan ink are ink cartridge recording inks. An ink cartridge comprising a set of yellow ink, magenta ink, and cyan ink. An ink jet recording apparatus comprising an ink cartridge and an ink ejecting means, wherein ink for ink jet recording is ejected from the ink ejecting means, wherein the ink cartridge is the ink cartridge according to claim 12. apparatus. Furthermore, including a rubber member,
The inkjet recording apparatus according to claim 13, wherein the rubber member includes ethylene propylene rubber.

Images