JP2007191644A - Ink composition, ink set, recording method, and recorded product by the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set providing an image having excellent hue, light resistance and gas fastness, and hardly having defects as the image quality such as bleeding of a fine line, and having improved image preservability under a severe condition. <P>SOLUTION: The ink set has a yellow ink composition containing, for example, a compound of general formula (1), and C.I Direct Yellow 132 and/or C.I. Direct Yellow 86 as yellow dyes. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink composition, an ink set, a recording method, and a recorded matter thereby, and in particular, is excellent in hue, light resistance, and gas fastness of an image obtained, has no defects in image quality such as fine line bleeding, and is severe. The present invention relates to an ink composition, an ink set, a recording method, and a recorded matter with improved image storability under various conditions.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used.

  The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.

  Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force.

  As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.

  For dyes used in such inks for ink jet recording, the solvent has good solubility or dispersibility, high-density recording is possible, hue is good, light, heat, in the environment Fast against active gases (NOx, ozone and other oxidizing gases, SOx, etc.), excellent fastness to water and chemicals, good fixability to image-receiving materials, and low bleeding. It is required that the ink has excellent storability, has no toxicity, has high purity, and can be obtained at low cost.

  However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, when printing on an image receiving material having an ink receiving layer containing porous white inorganic pigment particles, it is robust against light, humidity, and heat, and an oxidizing gas such as ozone in the environment. It is strongly desired to be robust against the above.

For example, Patent Documents 1 and 2 propose improvement of the light resistance of an image. Further, for example, Patent Documents 3 and 4 propose the improvement of ozone resistance. On the other hand, for the purpose of improving color reproducibility, C.I. I. Direct Yellow 86 and C.I. I. A yellow ink composition used in combination with direct yellow 132 has also been proposed (see Patent Document 5).
JP 2000-290559 A JP 2001-288392 A International Publication WO02 / 060994 Pamphlet JP 2002-371214 A JP 2000-154344 A

However, the above-described conventional techniques have room for improvement in the hue, light resistance, gas fastness, image quality, and image storage stability of the obtained image.
Accordingly, an object of the present invention is an ink for ink jet recording which is excellent in hue, light resistance and gas fastness of an image obtained, has no image quality defects such as fine line bleeding, and has improved image storability under severe conditions. It is to provide a composition and an ink jet recording method.

  The present inventors have found that the above-mentioned problems can be solved by combining a yellow dye having a specific structure that has not been known so far with CI direct yellow 132 and / or CI direct yellow 86, and to complete the present invention. It came. The present invention is as follows.

1) An ink composition comprising at least one selected from the group consisting of a compound represented by the following general formula (Y-I) and a salt thereof, and CI direct yellow 132 and / or CI direct yellow 86 object.
Formula (Y-I):

  In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of

2) The ratio of use of at least one selected from the group consisting of the compound represented by (Y-I) and a salt thereof and CI direct yellow 132 and / or CI direct yellow 86 is the former: latter mass ratio. The ink composition as described in 1) above, wherein the ratio is 1: 9 to 9: 1.
3) An ink set comprising the ink composition described in 1) or 2) above.
4) A recording method comprising applying the ink composition according to 1) or 2) onto a recording medium.
5) A recording method comprising recording by discharging droplets of the ink composition described in 1) or 2) onto a recording medium.
6) Recorded matter recorded using the recording method described in 4) or 5) above.

In the present invention, the following embodiments are also preferable.
That is,
<1>
An ink set comprising at least a yellow ink composition, a magenta ink composition, a cyan ink composition and a black composition, wherein the yellow ink composition is represented by the general formula (YI) as a yellow dye. An ink set comprising: CI direct yellow 132 and / or CI direct yellow 86; and at least one selected from the group consisting of the above compounds and salts thereof.

<2>
The yellow ink composition represented by the general formula (Y-I) has the following general formula (Y-1), general formula (Y-2), general formula (Y-3), and general formula (Y-4). Or it is at least 1 sort (s) chosen from the group which consists of a compound represented with general formula (Y-5), and its salt, It is the ink set as described in said <1> characterized by the above-mentioned.
General formula (Y-1):

式中、Ｒ_１、Ｒ_２、Ｒ_１１、Ｒ_１２、Ｘ_１、Ｘ_２、Ｚ_１、及びＺ_２は一価の基を示し、Ｌ_１は２価の連結基を示し、Ｇ_１、Ｇ_２はそれぞれ独立に５〜８員含窒素ヘテロ環を構成する原子団を示し、Ｍは水素原子またはカチオンを示す。ｍ_２１、ｍ_２２は、それぞれ独立に０〜３の整数を表す。
一般式（Ｙ−３）： In the formula, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, and G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3.
General formula (Y-2):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₁ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₂₁ and m ₂₂ each independently represent an integer of 0 to 3.
General formula (Y-3):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group, L ₂ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.
General formula (Y-4):

In the formula, R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₃ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.
General formula (Y-5):

In the formula, R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group, L ₄ represents a divalent linking group, and G ₁ , G ₂ independently represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

<3>
Formula (Y-1), Formula (Y-2), the general formula (Y-3), Formula (Y-4), the general formula (Y-5), G, composed of _{G 1} and _{G 2} The ink set according to <2>, wherein the nitrogen-containing heterocycle is an S-triazine ring.

<4>
The ink set according to <2>, wherein the dye represented by the general formula (Y-1) is a dye represented by the following general formula (Y-6).
General formula (Y-6):

In the formula, R ₁ , R ₂ , Y ₁ and Y _{2 each} represent a monovalent group, and X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently 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 An aryl group, a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation.

<5>
The yellow ink composition according to <1> to <4> further includes at least one selected from the group consisting of a compound represented by the following general formula (Y-7) and a salt thereof as a colorant. The ink set according to any one of <1> to <4> above.
General formula (Y-7):

In the general formula (Y-7), A ₁ and A ₂ are a substituted or unsubstituted aryl group and / or a substituted or unsubstituted 5- or 6-membered heterocyclic diazo component A ₁ -NH ₂ , A _2-. It represents the residue of NH _2. R ₁ and R ₂ represent a monovalent group, G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m ₁ represents an integer of 0 to 3. However, General Formula (Y-7) has at least one ionic hydrophilic group. In the case where A ₁ and A ₂ represent the residues of the 5-membered heterocyclic diazo component A ₁ -NH ₂ and A ₂ -NH ₂ , the pyrazole ring is excluded.

<6>
In <5>, the yellow ink composition represented by the general formula (Y-7) contains at least one selected from the group consisting of a compound represented by the following general formula (Y-8) and a salt thereof. The ink set according to <5>, wherein the ink set is characterized by.
General formula (Y-8):

In formula _{(Y-8), A 1} , A 2, R 1, R 2 and M is a _{A 1, A 2, R 1} , R 2 and M as defined in formula (Y-7) is there. However, General Formula (Y-8) has at least one ionic hydrophilic group. In the case where A ₁ and A ₂ represent the residues of the 5-membered heterocyclic diazo component A ₁ -NH ₂ and A ₂ -NH ₂ , the pyrazole ring is excluded.

<7>
In <6>, the yellow-ink composition represented by the general formula (Y-8) contains at least one selected from the group consisting of a compound represented by the following general formula (Y-9) and a salt thereof. The ink set according to <6>, wherein the ink set is characterized by.
General formula (Y-9):

In General Formula (Y-9), R ₁ , R ₂ , R ₁₁ , and R _{12 each} represent a monovalent group. M represents a hydrogen atom or a cation. However, General Formula (Y-9) has at least one ionic hydrophilic group.

<8>
The yellow ink composition contains, as a colorant, at least one selected from the group consisting of the compounds represented by the general formulas (Y-I), (Y-1) to (Y-6) and salts thereof; or At least one selected from the group consisting of compounds represented by the general formulas (Y-I) and (Y-1) to (Y-6) and salts thereof, and further the general formulas (Y-7) to (Y- 9) As a colorant, at least one selected from the group consisting of the compound represented by 9) and a salt thereof is included; and the total amount of the colorant is 1 to 6% by mass with respect to the total mass of the yellow ink composition It is an ink set as described in any one of <1> to <7> above.

<9>
In the yellow ink composition, the concentration (% by mass) of the compound selected from the group consisting of the compounds represented by the general formulas (YI), (Y-1) to (Y-6) and salts thereof and the general The ratio of the compound represented by the formulas (Y-7) to (Y-9) and the concentration (% by mass) of the compound selected from the group consisting of salts thereof is in the range of 4: 1 to 10: 1. <5> to <8>, wherein the ink set is characterized by the above.

<10>
Any of the above <1> to <9>, wherein the magenta ink composition further contains at least one selected from the group consisting of a compound represented by the following formula (M-1) and a salt thereof as a colorant: Or the ink set described in 1.
General formula (M-1):

In the general formula (M-1), A represents a 5-membered heterocyclic group. B ¹ and B ² are each -CR ₁₃ =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. G, R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl substituted with a group or heterocyclic group And an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group may be further substituted. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.

<11>
The magenta ink composition represented by the general formula (M-1) is characterized by containing at least one selected from the group consisting of a compound represented by the following general formula (M-2) and a salt thereof. The ink set as described in <10> above, wherein
General formula (M-2):

In the general formula (M-2), A, B 1, B 2, R 11 and _{R 12,} A in the formula (M-1), at B _1, B _{2, R 11} and _{R 12} as defined is there.
a and e each independently represents an alkyl group, an alkoxy group or a halogen atom. When a and e are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and May be further substituted. b, c, and d are each independently synonymous with R ₁ and R _2, and may be condensed with each other at a and b, or e and d. However, General Formula (M-2) has at least one ionic hydrophilic group.

<12>
The magenta ink composition represented by the general formula (M-2) is characterized by containing at least one selected from the group consisting of a compound represented by the following general formula (M-3) and a salt thereof. The ink set as described in <11> above, wherein
General formula (M-3):

In General Formula (M-3), Z ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, a heterocyclic group or an acyl group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , a, b, c, d, and e have the same meanings as those in the general formula (M-2). Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of the groups Z ₁₁ , Z ₁₂ and Q may further have a substituent. However, General Formula (M-3) has at least one ionic hydrophilic group.

<13>
The magenta ink composition includes two types of magenta ink compositions having different color densities, and at least one magenta ink composition is represented by the general formulas (M-1), (M-2), and (M-3). The ink set according to any one of the above <10> to <12>, wherein the ink set comprises at least one selected from the group consisting of a compound represented by formula (1) and a salt thereof.

<14>
Of the two types of magenta ink compositions having different color densities, magenta ink compositions having a low color density are represented by the general formulas (M-1), (M-2), and (M-3). 0.5 to 3.5 mass with respect to the total mass of the magenta ink composition containing at least one selected from the group consisting of a compound and a salt thereof as a colorant and the total amount of the colorant having the low color density % Of the ink set according to <13>, wherein the ink set is contained.

<15>
Among the two types of magenta compositions having different color densities, the magenta ink composition having a high color density is a compound represented by the general formula (M-1), (M-2), or (M-3). And at least one selected from the group consisting of the salts thereof as a colorant, and the total amount of the colorant is 3 to 10% by mass with respect to the total mass of the magenta ink composition having the high color density <13> or <14>, wherein the ink set is characterized by the above.

<16>
In the two types of magenta ink compositions having different color densities, the colorant contained in the magenta ink composition having a low color density (mass%) and the colorant contained in the magenta ink composition having a high color density. The ink set according to any one of the above items <13> to <15>, wherein the ratio to the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8.

<17>
Any of the above <1> to <16>, wherein the cyan ink composition further contains at least one selected from the group consisting of a compound represented by the following formula (C-1) and a salt thereof as a colorant: Or the ink set described in 1.
General formula (C-1):

In the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ or —CO ₂ NV. ₁ V ₂ , —CO ₂ Z, —CO—Z or a sulfo group is represented. Here, each Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or represents an ionic hydrophilic group, each Each group may further have a substituent. a ₁ ~a ₄ and b ₁ ~b ₄ each represent the number of substituents of X ₁ to X ₄ and Y ₁ to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all of them are not 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4. M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group. As a group possessed as )

<18>
The cyan ink composition represented by the general formula (C-1) contains at least one selected from the group consisting of a compound represented by the following general formula (C-2) and a salt thereof. The ink set according to <17>.
General formula (C-2):

In the general formula (C-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, cyclo Alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfo group Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxy Carbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Suhoriru group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. l, m, n, p, q 1, q 2, q 3, q 4 each independently represents an integer of 1 or 2. M is synonymous with the case of general formula (C-1).

<19>
The cyan ink composition represented by the general formula (C-2) contains at least one selected from the group consisting of a compound represented by the following general formula (C-3) and a salt thereof. The ink set according to <17> or <18>.
General formula (C-3):

In general formula (C-3), Z ₁ , Z ₂ , Z ₃ , Z ₄ , 1, m, n, p and M are the same as Z ₁ , Z ₂ , Z ₃ , in general formula (C-2), Synonymous with Z ₄ , l, m, n, p and M.

<20>
In the compound represented by the general formula (C-3), M is a copper atom, and the Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently Z ₁₁ (the Z ₁₁ is − (CH ₂₎ represents a ₃ SO ₃ M _2, wherein _{M 2} represents an alkali metal atom) and / or _{Z 12} (wherein _{Z 12 is, - (CH 2). 3} SO 2 NHCH 2 CH (OH) CH _In addition, l, m, n, and p are 0 or 1, and the ink set according to any one of the above items <17> to <19>.

<21>
The ink set according to <20>, wherein M ₂ is Li.

<22>
The cyan ink composition contains, as a colorant, at least one selected from the group consisting of compounds represented by the general formulas (C-1), (C-2), and (C-3) and salts thereof. The total amount of the colorant is 1.0 to 10% by mass with respect to the total mass of the cyan ink composition, according to any one of the above <17> to <21> It is an ink set.

<23>
As the cyan ink composition, there are two kinds of cyan ink compositions having different color densities, and at least one cyan ink composition has the general formulas (C-1), (C-2), (C- 3) containing at least one selected from the group consisting of a compound represented by 3) and a salt thereof, and further containing at least one selected from the group consisting of a compound represented by the following general formula (C-4) and a salt thereof The ink set according to any one of the above items <17> to <22>, wherein
Formula (C-4):

In general formula (C-4), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ are each independently (= C (J ₁ )-or -N = ), (= C (J ₂ )-or -N =), (= C (J ₃ )-or -N =), (= C (J ₄ )-or -N =). J _{1 to} J ₄ each independently represents a hydrogen atom and / or a substituent. (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ), and at least one of the four rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} is a heterocycle .

<24>
In the cyan ink composition represented by the general formula (C-4), (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , Ring consisting of P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) {A ring: (A), B ring: (B), C ring: (C), D ring 24. The ink set according to claim 23, wherein the ink set is represented by the following general formula (I) when an aromatic ring is represented among four of (D)}.
Formula (I):

In general formula (I), * represents a bonding position with the phthalocyanine skeleton. G represents —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₂ Z ₃ , —CONZ ₂ Z ₃ , —CO ₂ Z ₁ , —COZ ₁ , or a sulfo group. t represents an integer of 1 to 4. Z ₁ may be the same or different, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl 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, or a substituted or unsubstituted heterocyclic group; Z2 and Z3 may be the same or different, and are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted Alternatively, it represents an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

<25>
In the cyan ink composition represented by the general formula (C-4), when any ring of A ring, B ring, C ring, and D ring is an aromatic ring, at least one aromatic ring is The ink set according to <7> or <8>, which is represented by the following general formula (II):
General formula (II):

  In general formula (II), * represents a bonding position with the phthalocyanine skeleton. G is synonymous with the said general formula (I). t1 is 1 or 2.

<26>
In the cyan ink composition represented by the general formula (C-4), (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , Ring consisting of P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) {A ring: (A), B ring: (B), C ring: (C), D ring : (D)} The ink set according to any one of <23> to <25>, wherein at least one heterocycle is a nitrogen-containing heterocycle.

<27>
Of the two types of cyan ink compositions having different color densities, cyan ink compositions having a low color density are those represented by the general formulas (C-1), (C-2), (C-3) and (C- 4) at least one selected from the group consisting of the compound represented by 4) and a salt thereof as a colorant, and the total amount of the colorant is 0.4 to 0.4 based on the total mass of the cyan ink having the low color density. The ink set according to any one of <17> to <26>, wherein the ink set is contained in an amount of 3.0% by mass.

<28>
Of the two types of cyan ink compositions having different color densities, a cyan ink composition having a high color density is represented by the general formulas (C-1), (C-2), and (C-3) as a colorant. 2.0 to 10 with respect to the total mass of the cyan ink composition containing at least one selected from the group consisting of the compound represented by the formula (I) and a salt thereof as a colorant and the total amount of the colorant having the high color density. The ink set according to any one of <17> to <27>, wherein the ink set is contained in an amount of 0.0% by mass.

<29>
In the two cyan ink compositions having different color densities, the colorant contained in the cyan ink composition having a high color density and the density (mass%) of the colorant contained in the cyan ink composition having a low color density. The ink set according to any one of the above items <17> to <28>, wherein the ratio to the concentration (mass%) of the agent is in the range of 1: 2 to 1: 8.

<30>
Of the two cyan ink compositions having different color densities, the cyan ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (C-2) and a salt thereof. In the above, Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a mixture selected from Z ₁₁ or Z ₁₂ and the whole cyan dye represented by the general formula (C-3) the molar ratio of the _{Z 11} and the _{Z 12} contained in the _above <18>, which is a dye mixture consisting mainly of _{Z 11 / Z 12 = 3/} 1 ~ <29> either 1 It is an ink set as described in above.

<31>
Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of the compound represented by formula (C-2) and a salt thereof. In the above, Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a mixture selected from Z ₁₁ or Z ₁₂ and the whole cyan dye represented by the general formula (C-3) the molar ratio of the _{Z 11} and the _{Z 12} contained in the _above <18>, which is a dye mixture consisting mainly of _{Z 11 / Z 12 = 2/} 2 ~ <30> either 1 It is an ink set as described in above.

<32>
Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of a compound represented by the following general formula (C-4) and a salt thereof. The ink set according to any one of <23> to <31>, wherein the ink set comprises:

<33>
Furthermore, the ink set according to any one of the above items <1> to <32>, further comprising a black ink composition.

<34>
<1> to <33>, wherein the black ink composition contains at least one selected from the group consisting of a compound represented by the following formula (B-1) and a salt thereof as a black dye. The ink set according to any one of the above.
General formula (B-1):

In the general formula (B-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =. V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or aryl Sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or sulfo Represents a group, and each group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or An arylsulfonyl group and a sulfamoyl group are represented, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

<35>
The black ink composition represented by the general formula (B-1) contains at least one selected from the group consisting of a compound represented by the following general formula (B-2) and a salt thereof. <34>.
General formula (B-2):

In the general formula (B-2), X represents an N atom or ═CW ₁ —. W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1, T 2} , R 41 and _{R 42} is an _A in the general formula (B-1), and _{V 1, T 1, T 2} , R 41 and _{R 42} synonymous.
W is synonymous with V ₁ in the general formula (B-1).

<36>
The black ink composition represented by the general formula (B-2) contains at least one selected from the group consisting of a compound represented by the following general formula (B-3) and a salt thereof. <34> or <35> The ink set according to <35>.
General formula (B-3):

In the general formula (B-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ are V ₁ , W, X, T ₁ in the general formula (B-2), the same meaning as T _{2, R 41} and _{R 42.} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a monovalent group.

<37>
The black ink composition represented by the general formula (B-3) is represented by the group consisting of a compound represented by the following general formula (B-4) and a salt thereof, and / or the following general formula (B-5). The ink set according to any one of <34> to <36>, wherein the ink set contains at least one selected from the group consisting of a compound and a salt thereof.
General formula (B-4):

In the general formula (B-4),
R ₄₃ has the same meaning as _{R 43} in the general formula (B-1). R ₄₄ has the same meaning as _{R 44} in the general formula (B-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (B-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in the above formula (B-3). W is synonymous with W in the general formula (B-3). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.
General formula (B-5):

R ₄₃ has the same meaning as _{R 43} in the general formula (B-1). R ₄₄ has the same meaning as _{R 44} in the general formula (B-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (B-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in the above formula (B-3). W is synonymous with W in the general formula (B-3). W ₁₁ has the same meaning as _{W 11} in the general formula (B-2). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.

<38>
<34> The group consisting of at least one compound selected from the group consisting of the compound represented by the general formula (B-1) and a salt thereof and a salt thereof represented by the following general formula (B-11): The ink set according to any one of <1> to <37>, which contains at least one selected from the group consisting of:
General formula (B-11):

In General Formula (B-11), G ₁ and G ₂ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group, and K represents an arbitrary substituent. L represents a divalent linking group. However, General Formula (B-11) has at least one ionic hydrophilic group.

<39>
At least one selected from the group consisting of a compound represented by the general formula (B-11) and a salt thereof is at least one selected from the group consisting of a compound represented by the following general formula (B-12) and a salt thereof. It is an ink set as described in said <38> characterized by containing.
General formula (B-12):

In General Formula (B-12), G ₁ , G ₂ , G ₃ and G ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁ represents a divalent linking group. However, General Formula (B-11) has at least one ionic hydrophilic group.

<40>
At least one selected from the group consisting of a compound represented by the general formula (B-12) and a salt thereof is at least one selected from the group consisting of a compound represented by the following general formula (B-13) and a salt thereof. The ink set according to any one of <38> to <39>, wherein the ink set comprises:
General formula (B-13):

In the general formula (B-13), E ₁ , E ₂ , E ₃ and E ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁₁ represents a divalent linking group. However, General Formula (B-11) has at least one ionic hydrophilic group.

<41>
At least one selected from the group consisting of a compound represented by the general formula (B-13) and a salt thereof is at least one selected from the group consisting of a compound represented by the following general formula (B-14) and a salt thereof. The ink set according to any one of <38> to <40>, wherein the ink set comprises:
General formula (B-14):

In General Formula (B-14), A ring, B ring, and C ring each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ each independently represents a hydrogen atom or a substituent. . However, General Formula (B-14) has at least one ionic hydrophilic group. Q ₁ and Q ₂ each independently represent a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group.

<42>
<1>-<41> An ink cartridge characterized in that the ink set described in any one of (1) to <41> is accommodated integrally or independently.

<43>
<42> An ink jet printer, wherein the ink cartridge according to <42> is loaded.

<44>
<1> to <41> An ink jet recording method, wherein recording is performed using the ink set according to any one of <1> to <41> or the ink cartridge according to <42>.

<45>
Image formation using the ink set described in any one of <1> to <41> or the ink cartridge described in <42> on an image receiving material having an ink receiving layer containing a white inorganic pigment on a support. This is an ink jet recording method.

<46>
A recorded matter recorded using the ink set according to any one of <1> to <41> or the ink cartridge according to <42>.

<47>
<1> to <41> A method for improving discoloration of a colored image material formed using the ink set according to any one of <41> or the ink cartridge according to <42>.

  According to the present invention, the ink obtained is superior in hue, light resistance and gas fastness of the image obtained compared with the prior art, has no image quality defects such as fine line bleeding, and has improved image storage stability under severe conditions. Set can be offered.

The ink set of the present invention includes a plurality of hue inks and includes at least a yellow ink composition.
The ink set according to the first aspect of the present invention includes a yellow ink composition, a magenta ink composition, and a cyan ink composition.

  The yellow composition of the present invention contains at least one selected from the group consisting of the dyes of the above general formulas (Y-I) and (Y-1) to (Y-6) as a colorant, and, in some cases, yellow- The colorant of the composition contains at least one selected from the group consisting of dyes represented by the general formulas (Y-7) to (Y-9).

  The ink set according to the second aspect of the present invention is the ink set according to the first aspect described above, wherein at least two magenta ink compositions having different color densities as the magenta ink composition as desired, that is, at least a dark magenta ink composition. And a light magenta ink composition, and at least one magenta ink composition contains at least one dye of the general formulas (M-1) to (M-3). In particular, the light magenta ink composition preferably contains at least one dye of the above formulas (M-1) to (M-3) as a colorant.

  The ink set according to the third aspect of the present invention is the ink set according to the first aspect or the second aspect, wherein at least two kinds of cyan ink compositions having different color densities as the cyan ink composition, if desired, An ink set comprising at least two kinds of a dark cyan ink composition and a light cyan ink composition, and at least one kind of cyan ink composition is represented by the general formulas (C-1) to (C-3) and / or the general It contains at least one kind of dye of formula (C-4). In particular, the light cyan ink composition preferably contains at least one of the dyes of the above formulas (C-1) to (C-3) and / or the above general formula (C-4) as a colorant (hereinafter referred to as “color cyan”). The magenta and cyan ink compositions having a high color density are referred to as “dark magenta ink composition” and “dark cyan ink composition”, respectively. The magenta and cyan ink compositions having low color density are respectively referred to as “light magenta ink composition”. And “light cyan ink composition”).

  The ink set according to the fourth embodiment of the present invention is the ink set according to the first, second, or third aspect, further having a black ink composition. The black dye used in the black ink composition is preferably at least one selected from the group consisting of dyes of the general formulas (B-1) to (B-5). In particular, the compounds represented by the formulas (B-4) to (B-5) and salts thereof, in addition to the compounds represented by the general formulas (B-11) to (B-14) and By using the salt (hereinafter also referred to as the dyes of formulas (B-11) to (B-14)), an image having excellent contrast and excellent light resistance and ozone resistance can be obtained. More preferred.

  Any of the ink sets of the present invention is used in a recording method using an ink composition. Examples of a recording method using an ink composition include an ink jet recording method, a recording method using a writing instrument such as a pen, various other types of printing, and the like. A printing method is mentioned. The ink set of the present invention is particularly preferable as an ink set used in an ink jet recording method.

  Each ink composition contained in the ink set of the present invention will be described. First, the colorant contained in each ink composition will be described below for each color ink composition. In the ink set of the present invention, by using a dye having a specific chemical structure as a colorant in each color ink composition, the light resistance and ozone resistance of the ink set as a whole can be made excellent.

  The colorant used in the yellow-ink composition constituting the ink set of the present invention will be described.

[Azo dye]
Here, Hammett's substituent constant σp value used in the present specification will be described briefly. Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compounds represented by the general formulas (I) and (1) to (6) of the present invention are not benzene derivatives, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

  The azo dye in the present invention is an azo dye represented by the general formulas (Y-I) and (Y-1) to (Y-6).

  Hereinafter, the general formula (Y-I) will be described in detail.

  In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3.

  When n is 1, R, X, Y, Z, Q, and G represent a monovalent group, and represent a monoazo dye shown in parentheses.

  When n is 2, R, X, Y, Z, Q, and G represent a monovalent or divalent substituent. However, at least one represents a divalent substituent, and represents a bis-type azo dye of the dye shown in parentheses.

  When n is 3, R, X, Y, Z, Q, and G represent a monovalent, divalent, or trivalent substituent. However, at least two represent a divalent substituent, or at least one represents a trivalent substituent, and represents a tris-type azo dye of a dye shown in parentheses.

  Hereinafter, the general formula (YI) will be described in more detail.

  In the general formula (Y-I), preferable examples of the substituent of G are preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group. Are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine, thiazoline and sulfolane.

  When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

  C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butyl) Phenyl, 2,4-di-t-amylphenyl), hetero-2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2 -Methoxyethoxy, 2-methylsulfonylethoxy), aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyl) Oxy, acylamino groups (eg, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), anilino groups ( For example Phenylamino, 2-chloroanilino), ureido groups (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino groups (eg, N, N-dipropylsulfamoylamino), alkylthio groups (eg, , Methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino) Alkylsulfonylamino group and arylsulfonylamino group (for example, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutyl) Carbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (for example, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl) ), An alkyloxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4- Methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenyl) Carbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group ( For example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, , Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg Carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  In the general formula (Y-I), examples of preferred substituents of Q, R, X, Y and Z will be described in detail.

  When Q, R, X, Y and Z represent a monovalent group, the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. 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, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

  Hereinafter, Q, R, X, Y, and Z will be described in more detail.

  The halogen atom represented by Q, R, X, Y and Z represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

  The alkyl group represented by Q, R, X, Y and Z 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 substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is preferable. Examples of the alkyl group include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.

  The cycloalkyl group represented by Q, R, X, Y and Z 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 include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

  The aralkyl group represented by Q, R, X, Y and Z includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aralkyl include benzyl and 2-phenethyl.

  The alkenyl group represented by Q, R, X, Y and Z represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Preferred examples include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

  The alkynyl group represented by Q, R, X, Y and Z is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

  The aryl group represented by Q, R, X, Y and Z is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoyl. Aminophenyl. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent.

  The heterocyclic group represented by Q, R, X, Y and Z 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. A group, which may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic group include, but are not limited to, substitution positions. Pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

  The alkoxy group represented by Q, R, X, Y and Z includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

  The aryloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

  The silyloxy group represented by Q, R, X, Y and Z is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

  The heterocyclic oxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

  The acyloxy group represented by Q, R, X, Y and Z is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An oxy group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group which can further have a substituent. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

  The carbamoyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

  The alkoxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

  The aryloxycarbonyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples thereof include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

  The amino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of the group include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

  The acylamino group represented by Q, R, X, Y and Z is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

  The aminocarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

  The alkoxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further substituted. Examples thereof include the same substituents as mentioned when the group can be included. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

  The aryloxycarbonylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

  The sulfamoylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups represented by Q, R, X, Y and Z are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. An amino group is preferable, and examples of the substituent include the same substituents as those exemplified when G is a group that can further have a substituent. Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

  The alkylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

  The arylthio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. As an example of the substituent, the G may further have a substituent. And the same substituents as mentioned when they are small groups. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

  The heterocyclic thio group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

  The sulfamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

  The alkyl and arylsulfinyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

  The alkyl and arylsulfonyl groups represented by Q, R, X, Y and Z are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, Examples of the substituent include the same substituents as those exemplified when G is a group capable of further having a substituent. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

  The acyl group represented by Q, R, X, Y and Z is 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, A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable, and examples of the substituent include a group in which G can further have a substituent. Examples are the same as the substituents sometimes mentioned. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

  The aryloxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. As an example of the substituent, the above G is further a substituent. Examples thereof include the same substituents as those exemplified when the group is capable of having. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

  The alkoxycarbonyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. As an example of the substituent, the above G further has a substituent. And the same substituents as mentioned when they are possible groups. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

  The carbamoyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

  The phosphino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

  The phosphinyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

  The phosphinyloxy group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

  The phosphinylamino group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. The same thing as the substituent which was mentioned when it was a group which can have a substituent is mentioned. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

  The silyl group represented by Q, R, X, Y and Z is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. As an example of the substituent, G may further have a substituent. The same substituents as mentioned when possible are listed. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

  Examples of the azo group represented by Q, R, X, Y, and Z include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. I can do it.

  Examples of the imide group represented by Q, R, X, Y, and Z include N-succinimide and N-phthalimide.

When Q, R, X, Y and Z represent a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene) and an alkenylene group (eg, ethenylene, propylene). Nylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1, 3,5-triazine-2, 4-diyl group, pyrimidine-2, 4 -Diyl group, pyrimidine-4,6-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR'- (R 'is a hydrogen atom, alkyl group or aryl group) _{, -S -, - SO 2 -} , - SO- , or a combination thereof (e.g., _{-NHCH 2 CH 2 NH -, -} NHCONH- , etc.) is good is Arbitrariness.

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

  Examples of the substituent are the same as those described for G above.

  The alkyl group and aryl group for R ′ have the same meanings as the examples of the substituent for G.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

When Q, R, X, Y and Z represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. (For example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.).

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (Y-I), preferred examples of n are 1 or 2, with 2 being particularly preferred.

  In the general formula (Y-I), a preferred example of the substituent for X is an electron-withdrawing group. In particular, it is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and more preferably an electron-withdrawing group having a σp value of 0.30 or more. The upper limit is 1.0 or less electron withdrawing group.

  Specific examples of X which is an electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphono group Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, A halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a heterocyclic group, a halogen atom, Azo group or selenocyane Group.

  Preferred examples of X include 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, an alkyloxycarbonyl group having 2 to 12 carbon atoms, and 7 to 18 carbon atoms. Aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, 6 to 6 carbon atoms 18 arylsulfonyl groups, C 0-12 sulfamoyl groups, C 1-12 halogenated alkyl groups, C 1-12 halogenated alkyloxy groups, C 1-12 halogenated alkylthio groups, carbon A halogenated aryloxy group having 7 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms substituted with two or more other electron-withdrawing groups having a σp of 0.20 or more, Fine nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

  More preferably, they are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms.

  Particularly preferable as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and the most preferable one is a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms. It is.

  In the general formula (YI), preferred examples of the substituent for Z are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;

  Detailed examples of the substituent represented by Z are the same as the corresponding examples of the substituent described in the example of the heterocyclic group represented by G, and preferred examples are also the same.

  A particularly preferred substituent represented by Z is a substituted aryl group or a substituted heterocyclic group, and among these, a substituted aryl group is particularly preferred.

  In the general formula (YI), preferred examples of the substituent for Q are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted group. The arylsulfonyl group is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group, and particularly preferably a hydrogen atom.

  In general formula (YI), R represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon number. A heterocyclic group having 4 to 12 carbon atoms is preferable. Among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, particularly a secondary or tertiary alkyl group is preferable, and a t-butyl group is most preferable. preferable.

  In general formula (Y-I), Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted group. A heterocyclic group having 4 to 12 carbon atoms in total is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms and / or a branched alkyl group is preferable, and a hydrogen atom or an alkyl having 1 to 8 carbon atoms is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

  Regarding the preferred combination of substituents of the dye represented by the general formula (Y-I) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferred combination as the dye represented by the general formula (Y-I) of the present invention includes the following (A) to (G).

(I) G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) R is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heterocyclic ring having 4 to 12 carbon atoms in total. Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is most preferable.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon group having 4 to 12 carbon atoms. Among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, and a hydrogen atom or an alkyl group having 1 to 8 is particularly preferable. Most preferred.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted aryl group or a substituted heterocyclic group, and among them, a substituted aryl group is particularly preferred.

(F) Q is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, particularly a hydrogen atom, A substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group is preferable, and a hydrogen atom is particularly preferable among them.

(G) n represents an integer of 1 to 3, preferably 1 or 2, and most preferably 2.

  Of the azo dyes represented by the general formula (Y-I), dyes represented by the following general formulas (Y-1) to (Y-5) are preferable.

Hereinafter, the general formula (Y-1) will be described in detail.
General formula (Y-1)

R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.
The monovalent group represents a hydrogen atom or a monovalent substituent. As an example of a monovalent substituent, it is synonymous with the monovalent substituent example of R, X, Y, and Z in the said general formula (I), and its preferable example is also the same. m ₁ represents an integer of 0 to 3.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ will be described in more detail.

Examples of the substituents for R ₁ and R ₂ are independently the same as the examples of R in the general formula (Y-I), and preferred examples are also the same.

Examples of substituents for Y ₁ and Y ₂ are independently the same as the examples of Y in the general formula (Y-I), and preferred examples are also the same.

Examples of substituents for Z ₁ and Z ₂ are independently the same as the examples of Z in the general formula (Y-I), and preferred examples are also the same.

Hereinafter, the G and m ₁ will be described in more detail.

  G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

  Preferred examples of the 5- to 8-membered nitrogen-containing heterocycle represented by G are S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, and among them, S-triazine A ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

m ₁ represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of the preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

  Hereinafter, the M will be described in more detail.

  M represents a hydrogen atom or a cation.

The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-1) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-1) of the present invention includes the following (A) to (F).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted group. Alternatively, an unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is most preferable.

(E) G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and preferable examples of the 5- to 8-membered nitrogen-containing heterocycle include S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, and pyridine ring. , An imidazole ring, a pyrazole ring, or a pyrrole ring, among which an S-triazine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is more preferable, and an S-triazine ring is most preferable.

(F) m ₁ represents an integer of 0 to 3, and when the —OM group is substitutable in the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferred, Among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

(G) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

Hereinafter, the general formula (Y-2) will be described in detail.
General formula (Y-2)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₁ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ , 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-2) will be described in more detail.

In the general formula (Y-2), preferable examples of the substituent for R ₁ and R ₂ are the same as the examples of the substituent for R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (Y-1). The preferred examples are also the same.

In Formula (Y-2), preferable examples of the substituents of _{X 1} and _{X 2} are the same as the examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In Formula (Y-2), preferable examples of the substituents of _{Z 1} and _{Z 2} are the same as the examples of the substituents of _{Z 1} and _{Z 2} described for formula (Y-1), preferred examples are also the same It is.

Preferred examples of Formula (Y-2) in, G ₁ and G ₂ are the same as the examples of G described for Formula (Y-1), and preferred examples thereof are also the same.

In the general formula (Y-2), m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and in the structure of a preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ , − When the OM group can be substituted, 0 to 2 are preferable, and 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are most preferable.

  In general formula (Y-2), the preferable example of M is synonymous with the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In the general formula (Y-2), preferred examples of the substituent for R ₁₁ and R ₁₂ are the same as the examples of the substituents for R ₁ , R ₂ , Y ₁ , and Y ₂ described in the general formula (Y-1). Preferred examples are -OM group (M is a hydrogen atom or cation), substituted or unsubstituted amino group; alkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, substituted or unsubstituted Examples thereof include a substituted alkylthio group having 1 to 12 carbon atoms and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms.

In the general formula (Y-2), the divalent linking group represented by L ₁ is an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene. Group (eg, ethynylene, propynylene), arylene group (eg, phenylene, naphthylene), divalent heterocyclic group (eg, 6-chloro-1, 3,5-triazine-2, 4-diyl group, pyrimidine-2, 4-diyl group, pyrimidine- 4,6-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl), -O-, -CO-, -NR- (R is a hydrogen atom, alkyl group or aryl group), -S-,- It is preferably SO ₂ —, —SO— or a combination thereof (for example, —NHCH ₂ CH ₂ NH—, —NHCONH—, etc.).

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

Examples of the substituent are the same as the substituents of _{R 1,} R 2, _{Y 1} and _{Y 2} in the formula (Y-1).

The alkyl group and aryl group of R are synonymous with the substituent examples of R ₁ , R ₂ , Y ₁ and Y _{2 in} the general formula (Y-1).

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-, -SO _2- or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.) and more preferably a.

  The total number of carbon atoms in the divalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  Regarding the preferred combination of substituents of the dye represented by formula (Y-2) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-2) of the present invention includes the following (A) to (H).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted Alternatively, an unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₂₁ and m ₂₂ each independently represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₁ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, the general formula (Y-3) will be described in detail.
General formula (Y-3)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , and Y ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₂ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₃₁ and m ₃₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-3) will be described in more detail.

In formula _{(Y-3), R 1} , R 2, Y 1, and preferred examples of the substituents of _{Y 2} are, _R 1 described for Formula _{(Y-1), R 2} , Y 1, and Y It is the same as the example of a substituent of ₂ , and a preferable example is also the same.

In formula (Y-3), preferable examples of the substituents of _{X 1} and _{X 2} are the same as examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-3), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In the general formula (Y-3), preferable examples of m ₃₁ and m ₃₂ are the same as the examples of m ₂₁ and m ₂₂ described in the general formula (Y-2), and preferable examples are also the same.

  In general formula (Y-3), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-3), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described above for Formula (Y-2), preferable examples thereof are also the same It is.

In General Formula (Y-3), the divalent linking group represented by L ₂ has the same meaning as the example of L ₁ described in General Formula (Y-2), and the preferred examples are also the same.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-3) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by formula (Y-3) of the present invention includes the following (i) to (h).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₃₁ and m ₃₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₂ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, the general formula (Y-4) will be described in detail.
General formula (Y-4)

R ₁₁ , R ₁₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₃ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₄₁ and m ₄₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-4) will be described in more detail.

In formula (Y-4), preferable examples of the substituents of _{Y 1,} and _{Y 2,} and examples of the substituents of the _R 1 described in the general formula _{(Y-1), R 2} , Y 1, and _{Y 2} It is the same, and a preferable example is also the same.

In formula (Y-4), preferable examples of the substituents of _{X 1} and _{X 2} are the same as examples of the substituents of _{X 1} and _{X 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-4), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In General Formula (Y-4), preferred examples of m ₄₁ and m ₄₂ are the same as the examples of m ₂₁ and m ₂₂ described in General Formula (Y-2), and preferred examples are also the same.

  In general formula (Y-4), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-4), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11, R 12} described above for Formula (Y-2), preferable examples thereof are also the same It is.

In the general formula (Y-4), examples of the divalent linking group represented by L ₃ are the same as the examples of L ₁ described in the general formula (Y-2), and preferred examples are also the same. .

  Regarding the preferred combination of substituents of the dye represented by formula (Y-4) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-4) of the present invention includes the following (A) to (H).

(I) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted Alternatively, an unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₄₁ and m ₄₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group (an alkylamino group having 1 to 12 carbon atoms, 6 carbon atoms) To an arylamino group having 1 to 18 carbon atoms), a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms, among which an unsubstituted amino group and carbon number An alkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is particularly preferable. Unsubstituted amino group, dialkylamino group having 1 to 12 carbon atoms, arylamino group having 6 to 18 carbon atoms, or substituted or unsubstituted An alkylthio group having from 1 to 12 carbons are preferred.

(H) L ₃ is an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, -S-, -SO-,- SO ₂ -, or a combination thereof (e.g., _{-SCH 2 CH 2 S -, -} SCH 2 CH 2 CH 2 S- , etc.), more preferably an alkylene group having 10 or less carbon atoms, having 6 to 10 carbon It is preferably an arylene group, —S—, —SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.), particularly 10 carbon atoms. following alkylene _{group, -SCH 2 CH 2 S -,} - SCH 2 CH 2 CH 2 S- and is preferably.

Hereinafter, Formula (Y-5) will be described in detail.
General formula (Y-5)

R ₁ , R ₂ , R ₁₁ , R ₁₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent a monovalent group.

  The monovalent group represents a hydrogen atom or a monovalent substituent.

L ₄ represents a divalent linking group.

G ₁ and G ₂ each independently represent an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle.

m ₅₁ and m ₅₂ each independently represents an integer of 0 to 3.

  M represents a hydrogen atom or a cation.

  Hereinafter, the general formula (Y-5) will be described in more detail.

In formula _{(Y-5), R 1} , preferred examples of the substituents of R 2, _{Y 1} and _{Y 2} are, _R 1 described for Formula _{(Y-1), R 2} , Y 1, and _{Y 2} And the preferred examples are also the same.

In formula (Y-5), preferable examples of the substituents of _{Z 1} and _{Z 2} are the same as examples of the substituents of _{Z 1} and _{Z 2} described for formula (Y-1), preferred examples are also the same It is.

In General Formula (Y-5), preferred examples of G ₁ and G ₂ are the same as the examples of G described in General Formula (Y-1), and preferred examples are also the same.

In General Formula (Y-5), preferred examples of m ₅₁ and m ₅₂ are the same as the examples of m ₂₁ and m ₂₂ described in General Formula (Y-2), and preferred examples are also the same.

  In general formula (Y-5), the preferable example of M is the same as the example of M demonstrated by the said general formula (Y-1), and its preferable example is also the same.

In formula _(Y-5), preferable examples of the substituents of _{R 11} and _{R 12} are the same as the examples of the substituents of _{R 11} and _{R 12} described for Formula (Y-2), preferable examples thereof are also the same It is.

In formula (Y-5), examples of the divalent linking group represented by L ₄ are the same as the examples of L ₁ described for Formula (Y-2), and preferred examples thereof are also the same .

  Regarding the preferred combination of substituents of the dye represented by formula (Y-5) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-5) of the present invention includes the following (A) to (H).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(C) Z ₁ and Z ₂ may be the same or different, and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted Alternatively, an unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is most preferable.

(D) G ₁ and G ₂ may be the same or different and each represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and a preferred example of the 5- to 8-membered nitrogen-containing heterocycle is an S-triazine ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, among which S-triazine ring, pyrimidine ring, pyridazine ring, or pyrazine ring is more preferable, and S-triazine ring is preferable. Most preferred.

(E) m ₄₁ and m ₄₂ each independently represent an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G ₁ and G ₂ can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 and m ₂ = 1 are particularly preferable.

(F) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(G) R ₁₁ and R ₁₂ may be the same or different, and —OM group (M is a hydrogen atom or a cation), a substituted or unsubstituted amino group; an alkylamino group having 1 to 12 carbon atoms, and 6 carbon atoms To an arylamino group having 1 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, and a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. Among them, an unsubstituted amino group and an alkylthio group having 1 to 12 carbon atoms are preferable. Are preferably an alkylamino group having 6 to 18 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 12 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms. An amino group, a dialkylamino group having 1 to 12 carbon atoms, an arylamino group having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon number 12 alkylthio group are preferable.

(H) L ₄ is a divalent linking group and preferably has an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably an electron-withdrawing group of 0.30 or more. It is an electron withdrawing group of 1.0 or less. Among them, an alkylsulfonyl group having 1 to 10 carbon atoms: {—SO ₂ — (CH ₂ ) n —O ₂ S—; an integer where n = 1 to 10}, an arylsulfonyl group having 6 to 18 carbon atoms: {— SO ₂ —Ar—O ₂ S—; Ar is preferably a substituted or unsubstituted aryl group}, most preferably an alkylsulfonyl group having 1 to 5 carbon atoms: {—SO ₂ — (CH ₂ ) n—O ₂ S-; n = integer of 1 to 5}.

Of the azo dyes represented by the general formula (Y-1), a dye represented by the general formula (Y-6) is preferable.
General formula (Y-6)

  Hereinafter, Formula (Y-6) will be described in detail.

R ₁ , R ₂ , Y ₁ and Y _{2 each} represent a monovalent group, and X ₁ and X ₂ each independently represent an electron-withdrawing group having a Hammett σp value of 0.20 or more. Z ₁ and Z ₂ are each independently 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 An aryl group or a substituted or unsubstituted heterocyclic group is shown. M represents a hydrogen atom or a cation.

Hereinafter, R ₁ , R ₂ , X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ and M will be described in detail.

Examples of the substituents of R _{1, R} 2, _{Y 1,} and _{Y 2} is the same as the examples of the substituents of the general formula _R 1 described in (Y-1) _in, R 2, _{Y 1,} and _{Y 2} There are also preferred examples.

Examples of the substituents of X ₁ and X ₂ are the same as examples of the substituents of X ₁ and X ₂ described in Formula (Y-1) and preferable examples thereof are also the same.

Examples of the substituents of Z ₁ and Z ₂ are the same as examples of the substituents of Z ₁ and Z ₂ described in Formula (Y-1) and preferable examples thereof are also the same.

  The example of M is the same as the example of M demonstrated in the said general formula (Y-1), and its preferable example is also the same.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  A particularly preferable combination as the coloring matter represented by the general formula (Y-6) of the present invention includes the following (A) to (E).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, more preferably 0.30 or more, The upper limit is 1.0 or less electron withdrawing group. Among these, a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms is preferable, and the most preferable one is a cyano group or 1 carbon atom. ˜12 alkylsulfonyl groups.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom is most preferable.

(D) Z ₁ and Z ₂ may be the same or different and are a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted group. Alternatively, an unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferable, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferable, and a substituted aryl group is most preferable.

(E) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

  In the present invention, it is represented by the general formulas (YI), (Y-1), (Y-2), (Y-3), (Y-4), (Y-5) and (Y-6). In the case where the compound needs hydrophilicity, it preferably has 2 or more ionic hydrophilic groups in the molecule, more preferably 2 to 10 ionic hydrophilic groups, and 3 to 6 It is particularly preferred to have one ionic hydrophilic group.

  However, when water is not used as a medium, it does not have to have an ionic hydrophilic group.

  The ionic hydrophilic group may be any as long as it is an ionic dissociation group. Specific examples include a sulfo group, a carboxyl group (including salts thereof), a hydroxyl group (may be a salt), a phosphono group (may be a salt), or quaternary ammonium.

A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable.
When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them Alkali metals are preferred. In particular, a lithium salt is preferred for the sulfo group, and a sodium salt and / or potassium salt is preferred for the carboxy group.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (Y-6-I) is preferable among the compounds represented by the said general formula (Y-6).
General formula (Y-6-I):

In formula (Y-6-I), R ₁ , R ₂ , Y ₁ , Y ₂ , W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ represents a monovalent group, and X ₁ and X ₂ each independently represents an electron-withdrawing group having a Hammett σp value of 0.20 or more. M represents a hydrogen atom or a cation. However, at least one of W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ , W ₂₅ is an ionic hydrophilic group or ionic hydrophilic It is a group having a group as a substituent.

  In the present invention, the general formula (Y-6-I) will be described in detail.

In the present invention, in the general formula (Y-6-I), W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are In formula (Y-6), it is synonymous with the example of the monovalent group demonstrated by Y < ₁ >, Y < ₂ >, Z < ₁ >, Z < ₂ >.

Preferred W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group , Alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (Including salts thereof), hydroxyl group (may be salt), phosphono group (may be salt) or quaternary ammonium, among which hydrogen atom, halogen atom, alkyl group, sulfo group (including salts thereof), A carboxyl group (including salts thereof) and a hydroxyl group (may be a salt) are preferable, and further a hydrogen atom, a sulfo group (their thereof) Salt), carboxyl groups (including salts thereof) are preferred, and in particular, at least one of W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ and W ₁₅ is a sulfo group (including salts thereof), carboxyl group ( Those salts), and at least one of W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ is preferably a sulfo group (including their salts) or a carboxyl group (including their salts).

In the present invention, in the general formula (Y-6-I), X1 and X2 have the same meanings as X ₁ and X _{2 in the} general formula (Y-6), and preferred examples are also the same.

In the present invention, the general formula _(Y-6-I), Y 1, Y 2 mother Formula (Y-6) in a _Y 1, _{Y 2} and synonymous, and preferred examples are also the same .

In the present invention, in formula _(Y-6-I), R 1, R 2 has the same meaning as _R 1, _{R 2} in Formula (Y-6), and preferred examples thereof are also the same.

  In the present invention, in the general formula (Y-6-I), M is synonymous with M in the general formula (Y-6), and preferred examples are also the same.

  A particularly preferable combination as the compound represented by the general formula (Y-6-I) of the present invention includes the following (A) to (F).

(I) R ₁ and R ₂ may be the same or different, and are preferably a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group, particularly preferably a secondary or tertiary alkyl group, t- A butyl group is most preferred.

(B) X ₁ and X ₂ may be the same or different, and a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms Preferred and most preferred is a cyano group.

(C) Y ₁ and Y ₂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms in total, Alternatively, a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total is preferable, and a hydrogen atom or a substituted or unsubstituted alkyl group is preferable, and among them, a hydrogen atom and a methyl group are most preferable.

(D) W ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ , W ₁₅ , W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and W ₂₅ are hydrogen atoms, halogen atoms, alkyl groups, sulfo groups (their salts are ), Carboxyl groups (including salts thereof) and hydroxyl groups (may be salts), hydrogen atoms, sulfo groups (including salts thereof), and carboxyl groups (including salts thereof) are particularly preferable. ₁₁ , W ₁₂ , W ₁₃ , W ₁₄ and W ₁₅ are each a sulfo group (including a salt thereof), a carboxyl group (including a salt thereof), and W ₂₁ , W ₂₂ , W ₂₃ , W ₂₄ and At least one of W ₂₅ is preferably a sulfo group (including salts thereof) or a carboxyl group (including salts thereof).

(E) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(F) In the present invention, the compound represented by the general formula (Y-3-I) preferably has two or more ionic hydrophilic groups in the molecule, and has 2 to 16 ionic hydrophilic groups. It is more preferable to have a group, and it is particularly preferable to have 3 to 5 ionic hydrophilic groups.

  The ionic hydrophilic group may be any as long as it is an ionic dissociation group. Specific examples include a sulfo group, a carboxyl group (including salts thereof), a hydroxyl group (may be a salt), a phosphono group (may be a salt), or quaternary ammonium. A sulfo group, a carboxyl group, or a hydroxyl group (including salts thereof) is preferable.

  When the ionic hydrophilic group is a salt, preferred counter cations include alkali metals (eg, lithium, sodium, potassium), ammonium, and organic cations (eg, pyridinium, tetramethylammonium, guanidinium), among them Alkali metals are preferred. In particular, a lithium salt is preferred for the sulfo group, and a sodium salt and / or potassium salt is preferred for the carboxy group.

  As for the preferred combination of substituents of the dye represented by the general formula (Y-6-I) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substitutions are possible. More preferred are compounds in which the group is the preferred group, and most preferred are compounds in which all substituents are the preferred groups.

The yellow ink composition of the present invention may further contain at least one selected from the group consisting of a compound represented by the following general formula (Y-7) and a salt thereof as a colorant.
General formula (Y-7):

In the general formula (Y-7), A ₁ and A ₂ are a substituted or unsubstituted aryl group and / or a substituted or unsubstituted 5- or 6-membered heterocyclic diazo component A ₁ -NH ₂ , A _2-. It represents the residue of NH _2. R ₁ and R ₂ represent a monovalent group, G represents an atomic group constituting a 5- to 8-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or a cation. m1 represents an integer of 0 to 3. However, General Formula (Y-7) has at least one ionic hydrophilic group. In the case where A ₁ and A ₂ represent the residues of the 5-membered heterocyclic diazo component A ₁ -NH ₂ and A ₂ -NH ₂ , the pyrazole ring is excluded.

In the present invention, preferable A ₁ and A _{2 in the} general formula (Y-7) will be described in detail.

The aryl group represented by A ₁ and A ₂ includes a substituted or unsubstituted aryl group. As the substituted or unsubstituted aryl group, an aryl group having 6 to 30 carbon atoms is preferable.

  Examples of the substituent of the aryl group include a halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxyl group (salt May be in the form of alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, amino group Carbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group (salt Alkyl, arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups. Examples thereof include a group and a silyl group.

The aryl group represented by A ₁ and A ₂ is more preferably a substituted phenyl group (the substituent is preferably a carboxyl group or a sulfo group).

The heterocycle of the heterocyclic group represented by A ₁ and A ₂ is preferably a 5-membered or 6-membered ring, which may be further condensed.

  Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. For example, pyridine, pyrazine, pyridazine, pyrimidine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzo Examples include thiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine and thiazoline.

  Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Thiadiazole, more preferably imidazole, benzoxazole, and thiadiazole, particularly thiadiazole (preferably 1,3,4-thiadiazole, 1,2,4-thiadiazole), among which 1,3,4 -Thiadiazole is most preferred.

  They may have a substituent, and examples of the substituent are the same as those of the aryl group described above.

  In the present invention, preferable G in the general formula (Y-7) will be described in detail.

  In the general formula (Y-7), preferred examples of the substituent for G are preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group. Are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine, thiazoline, sulfolane and the like.

  Further, G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, and among them, S-triazine A ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

  When the heterocyclic group is a group that can further have a substituent, the heterocyclic group may further have the following substituents.

  C1-C12 linear or branched alkyl group, C7-C18 linear or branched aralkyl group, C2-C12 linear or branched alkenyl group, C2-C12 linear Or a branched alkynyl group, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (the above groups having a branched chain are dissolved in a dye) Preferred are those having an asymmetric carbon, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), halogen atom (for example, chlorine atom, bromine atom), aryl group (for example, phenyl, 4-t-butyl) Phenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro Group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino group (eg, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino group (For example, Mechi Amino, butylamino, diethylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group ( For example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2- Carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and arylsulfonylamino groups (eg methylsulfonylamino, phenylsulfonylamino, p-toluenes) Phonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), A sulfonyl group (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), an alkyloxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl), a heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) 2-tetrahydropyranyloxy), azo groups (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy groups (for example, aceto Xy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide Group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio) ), Sulfinyl groups (eg 3-phenoxypropylsulfinyl), phosphonyl groups (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (example If, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

In the present invention, in the general formula (Y-7), preferable R ₁ and R ₂ will be described in detail.

R ₁ and R ₂ represent a monovalent group, and the monovalent group represents a hydrogen atom or a monovalent substituent. The monovalent substituent will be described in more detail. 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, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonyl Amino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, A silyl group, an azo group, or an imide group can be mentioned, and each may further have a substituent.

  Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups.

R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon number. A heterocyclic group having 4 to 12 carbon atoms is preferable. Among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, particularly a secondary or tertiary alkyl group is preferable, and a t-butyl group is most preferable. preferable.

  In the present invention, preferable M in the general formula (Y-7) will be described in detail.

M represents a hydrogen atom or a cation. The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

In the present invention, in the general formula (Y-7), preferable m ₁ will be described in detail.

m ₁ represents an integer of 0 to 3, and when the —OM group can be substituted in the structure of the preferred example of the 5- to 8-membered nitrogen-containing heterocycle represented by G, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 is particularly preferable.

  A particularly preferred combination as the compound represented by formula (Y-7) of the present invention includes the following (A) to (E).

In (i) the general formula _{(Y-7), A 1} , A 2 is preferably a 5- or 6-membered ring, which may be further condensed. Among them, a 5-membered or 6-membered nitrogen-containing heterocycle is preferable, and examples thereof include pyridine, pyrazine, pyridazine, pyrimidine, imidazole, benzimidazole, triazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole. More preferably, imidazole, benzoxazole, and thiadiazole are exemplified, and thiadiazole (preferably 1,3,4-thiadiazole, 1,2,4-thiadiazole) is particularly preferable, and among these, 1,3,4-thiadiazole is most preferable. .

(B) In the general formula (Y-7), a preferred example of the substituent for G is preferably a 5- to 8-membered heterocyclic group, and among them, a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic group. Heterocyclic groups are preferred, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Further, examples of the heterocyclic group include, but are not limited to, the substitution position. Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, sulfolane Etc. Further, G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring, and among them, S-triazine A ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(C) In General Formula (Y-7), R ₁ and R ₂ represent a monovalent group. The monovalent group represents a hydrogen atom or a monovalent substituent. Among them, particularly preferred are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group. An arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, or a heterocyclic group, and a hydrogen atom, an alkyl group Most preferred are groups, aryl groups, cyano groups, or alkylsulfonyl groups. More preferably, R 1 and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total group. A heterocyclic group having 4 to 12 carbon atoms is preferable, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a secondary or tertiary alkyl group is particularly preferable, and a t-butyl group is preferable. Is most preferred.

(D) In general formula (Y-7), M represents a hydrogen atom or a cation. The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

(E) In the above general formula (Y-7), m ₁ represents an integer of 0 to 3, and the structure of a preferred example of a 5- to 8-membered nitrogen-containing heterocycle represented by G can be substituted with an —OM group. In this case, 0 to 2 are preferable, and among them, 0 or 1 is preferable, and m ₁ = 1 is most preferable.

  Regarding the preferred combination of substituents of the dye represented by formula (Y-7) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (Y-8) is preferable among the compounds represented by the said general formula (Y-7).
General formula (Y-8):

In formula _{(Y-8), A 1} , A 2, R 1, R 2 and M is a _{A 1, A 2, R 1} , R 2 and M as defined in formula (Y-7) is there. However, General Formula (Y-8) has at least one ionic hydrophilic group.

  In the present invention, the general formula (Y-8) will be described in detail.

In the present invention, in formula _(Y-8), A 1, _{A 2,} the general formula (Y-7) in a _A 1, _{A 2} and synonymous, and preferred examples are also the same.

In the present invention, in formula _(Y-8), R 1, _{R 2,} the general formula (Y-7) in _{wherein R} 1, _{R 2} and synonymous, and preferred examples are also the same.

  In this invention, in the said general formula (Y-8), M is synonymous with M in the said general formula (Y-7), and its preferable example is also the same.

  Particularly preferred combinations as the compound represented by formula (Y-8) of the present invention include the following (A) to (D).

(I) In general formula (Y-8), A ₁ and A ₂ are preferably 5-membered or 6-membered nitrogen-containing heterocycles, and pyridine, pyrazine, pyridazine, pyrimidine, imidazole, benzimidazole, triazole, benzoxazole. , Thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole, more preferably imidazole, benzoxazole and thiadiazole, particularly thiadiazole (preferably 1,3,4-thiadiazole, 1,2,4- Thiadiazole) is preferred, and among these, 1,3,4-thiadiazole is most preferred.

(B) In general formula (Y-8), G is preferably a 5- to 8-membered nitrogen-containing heterocycle, and particularly an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, Or a pyrrole ring is preferable, and among them, an S-triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferable, and an S-triazine ring is most preferable.

(C) In general formula (Y-8), R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. Or a substituted or unsubstituted heterocyclic group having 4 to 12 carbon atoms in total, among which a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, particularly secondary or tertiary. Alkyl groups are preferred, and t-butyl groups are most preferred.

(D) In general formula (Y-8), M represents a hydrogen atom or a cation. The cation represented by M is an alkali metal ion, ammonium or a quaternary ammonium cation, and preferably Li, Na, K, NH ₄ , or NR ₄ . However, R is an alkyl group and an aryl group, and is the same as the examples of the alkyl group and aryl group represented by R and Y described above. Among them, preferable examples of the cation of M are Li, Na, K, or NH ₄ , and Li, Na, or K is particularly preferable.

  Regarding the preferred combination of substituents of the dye represented by formula (Y-8) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (Y-9) is preferable among the compounds represented by the said general formula (Y-8).
General formula (Y-9):

In General Formula (Y-7), R ₁ , R ₂ , R ₁₁ , and R ₁₂ represent a monovalent group. M represents a hydrogen atom or a cation. However, General Formula (Y-9) has at least one ionic hydrophilic group.

In the present invention, in the general formula (Y-9), preferable R ₁₁ and R ₁₂ are each independently an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or a cyano group. , Hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group ), Acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, a Thiol group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkyloxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyl group Examples thereof include a finyloxy group, a phosphinylamino group, a silyl group, an azo group, and an imide group, each of which may further have a substituent.

Particularly preferably, R ₁₁ and R ₁₂ are each independently a substituted alkyl group, a substituted aryl group, a substituted heterocyclic group, a substituted alkylthio group, a substituted arylthio group or a substituted heterocyclic thio group, and among them, a substituted aryl group or a substituted An arylthio group is preferred, and a substituted aryl group is particularly preferred.

In the present invention, in formula _(Y-9), R 1, _{R 2} has the same meaning as _R 1, _{R 2} in the general formula (Y-8), and preferred examples thereof are also the same.

  In this invention, in the said general formula (Y-9), M is synonymous with M in the said general formula (Y-8), and its preferable example is also the same.

  A particularly preferred combination as the compound represented by formula (Y-9) of the present invention includes the following (A) to (D).

(I) R ₁ and R ₂ may be the same or different and are substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted aryl groups having 6 to 18 carbon atoms, or substituted or unsubstituted An unsubstituted heterocyclic group having 4 to 12 carbon atoms is preferred, and among them, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferred, and a secondary or tertiary alkyl group is particularly preferred. A t-butyl group is most preferred.

(B) R ₁₁ and R ₁₂ may be the same or different, and are preferably a substituted alkyl group, a substituted aryl group, a substituted heterocyclic group, a substituted alkylthio group, a substituted arylthio group, or a substituted heterocyclic thio group. A substituted aryl group and a substituted arylthio group are preferred, and a substituted aryl group is particularly preferred.

(C) M is preferably a hydrogen atom or a cation, particularly preferably a hydrogen atom, an alkali metal ion, ammonium or a quaternary ammonium cation, and more preferably Li, Na, K, or NH ₄ .

(D) In the present invention, the compound represented by formula (Y-4) preferably has two or more ionic hydrophilic groups in the molecule, and has 2 to 16 ionic hydrophilic groups. It is further preferable to have 3 to 5 ionic hydrophilic groups.

The general formulas (Y-I), (Y-1), (Y-2), (Y-3), (Y-4), (Y-5), (Y-6), (Y-6) In the case of water-soluble dyes represented by I), (Y-7), (Y-8) and (Y-9), the maximum absorption wavelength of 380 to 490 nm in H ₂ O from the viewpoint of color reproducibility (λmax) is preferable, λmax of 400 to 480 nm is further preferable, and λmax is particularly preferably 420 to 460 nm.

  The colorant used in the yellow ink composition contained in the ink set of the present invention is selected from the group consisting of the compound represented by the general formula (Y-6-I) (dye of formula (Y-6-I)). It is preferable to include at least one selected. Further, according to circumstances, at least one selected from the group consisting of compounds represented by the general formulas (Y-7) to (Y-9) (dyes of formulas (Y-7) to (Y-9)) is further included. It is also preferable. Among these, it is most preferable to include at least one selected from the group consisting of compounds represented by the general formula (Y-6-I) (dyes of formula (Y-6-I)).

  By using at least one selected from the group consisting of dyes of the formula (Y-6-I) as the colorant of the yellow ink composition; the light resistance and ozone resistance of the ink compositions of other colors can be balanced Thus, the light resistance and ozone resistance of the entire ink set can be improved.

  In the present invention, the concentration of the colorant contained in the yellow ink composition can be appropriately determined according to the color value of the compound (dye) used as the colorant, but the above general formulas (Y-1) to (Y In the case where at least one selected from the group consisting of dyes of general formulas (Y-7) to (Y-9) is included in the yellow ink composition, generally, the above general formula ( Y-1) to (Y-6-I) and optionally the total amount of colorant selected from the group consisting of dyes of general formulas (Y-7) to (Y-9) in the yellow ink composition In addition, it is preferable to contain 1.0 to 6.0% by mass with respect to the total mass of the yellow ink composition. When the concentration of the total amount of the colorants contained in the yellow ink composition is 1.0% by mass or more, good color developability can be obtained, and the concentration of the total amount of the colorants is 6.0. By setting the content to not more than mass%, it is possible to improve the properties such as ejection properties from the nozzles required as an ink composition for use in the ink jet recording method, and to prevent clogging of the ink nozzles.

  As described above, general formulas (Y-7) to (Y-) together with at least one selected from the group consisting of the dyes of general formulas (Y-1) to (Y-6-I) as colorants for the yellow ink composition. When the dye of 9) is used, the total concentration (mass%) of the dye selected from the group consisting of the dyes of the above general formulas (Y-1) to (Y-6-I) in the yellow ink composition and the general formula The ratio of (Y-7) to (Y-9) to the concentration (% by mass) of the dye is preferably 4: 1 to 10: 1.

In the present invention, it is essential to use CI direct yellow 132 and / or CI direct yellow 86 in the yellow ink composition. By using these dyes together, the hue, light resistance and gas fastness of the resulting image are superior to those of the prior art, there are no image quality defects such as fine line bleeding, and image storage under severe conditions has been improved. An ink set can be provided. The use ratio of at least one selected from the group consisting of the compound represented by (Y-I) and a salt thereof and CI direct yellow 132 and / or CI direct yellow 86 is 1 as the mass ratio of the former: the latter. : It is preferable that it is 9-9: 1. More preferably, it is 3: 7 to 9: 1, and particularly preferably 5: 5 to 9: 1.
CI direct yellow 132 has the following structure.

C.I. Direct Yellow 86 has the following structure.

    In the formula, M represents H, Li, Na, K.

  Furthermore, in the present invention, in order to adjust the color tone of the yellow ink composition, other yellow dyes can be used in combination as long as the light resistance and ozone resistance are not significantly impaired.

Examples of the yellow dye used in combination include C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 196, 197, 199, 218, 219, 222, 227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 and the following general formula (Y-10), general formula (Y-11) and the like can be mentioned, but are not limited thereto.
Formula (Y-10);

Formula (Y-11);

(In the general formulas (Y-10) and (Y-11), K ₁ , K ₂ , K ₁₁ , and K ₂₁ independently represent CH ₃ , OCH ₃ , and Z and Z ′ represent independently And it has the structure of either of the following formula, and may mutually be the same or different.

  Here, M represents H, Li, Na, K, ammonium, or organic amines, and n is an integer of 1 or 2. )

  Next, the colorant used in the magenta ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the magenta ink composition is not limited to the colorant having a specific structure, but the light resistance / ozone resistance of the ink composition of other colors and the magenta ink composition It is preferable that the difference between light resistance and ozone resistance is small.

In the present invention, the magenta dye used as a colorant in the magenta ink composition is a compound selected from the group consisting of a compound represented by the following general formula (M-1) and a salt thereof.
General formula (M-1):

In the general formula (M-1), A represents a 5-membered heterocyclic group. B ¹ and B ² are each -CR ₁₃ =, - or represents _{CR 14} =, or either one is a nitrogen atom, the other represents _{-CR 13} = or _{-CR 14} =. R ₁₁ and R ₁₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl. Represents a group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. G, R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, nitro group, alkyl substituted with a group or heterocyclic group And an arylthio group, an alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a heterocyclic thio group or an ionic hydrophilic group. Each group may be further substituted. R ₁₃ and R ₁₁ , or R ₁₁ and R ₁₂ may be bonded to form a 5- to 6-membered ring. However, General Formula (M-1) has at least one ionic hydrophilic group.

  In the present invention, in the general formula (M-1), preferable examples of A include N, O, and S as examples of the hetero atom of the 5-membered heterocyclic ring. Preferably, it is a nitrogen-containing 5-membered heterocycle, and the heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. Examples of a preferable heterocyclic ring for A include a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, heterocyclic rings represented by the following general formulas (a) to (i) are preferable.

In the general formulas (a) to (i), Rm _{1 to} Rm ₂₀ have the same meaning as R ₁₃ or R ₁₄ in the general formula (M-1).

In the general formula (M-1), B ₁ and B ₂ each represent —CR ₁₃ ═ or —CR ₁₄ ═, or either one is a nitrogen atom and the other is —CR ₁₃ ═ or —CR _14. In the case where B ₁ and B ₂ represent —CR ₁₃ ═ or —CR ₁₄ ═, it is preferable in that a more excellent performance can be exhibited.

In the general formula (M-1), R ₁₁ and R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, A substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, and a substituted or unsubstituted arylsulfonyl group are preferable, and a hydrogen atom, a substituted aryl group, and a substituted heterocyclic group are more preferable. Among them, a substituted aryl group and a substituted Heterocyclic groups are particularly preferred. However, R ₁₁ and R ₁₂ are not simultaneously hydrogen atoms.

  In the general formula (M-1), G represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, or a heterocyclic oxy group. Group, an alkyl group or an aryl group or an amino group substituted with an aryl group or a heterocyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkyl and An arylthio group, a heterocyclic thio group or an ionic hydrophilic group is preferred. Each group may be further substituted.

  Furthermore, a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, or an acylamino group is preferable.

  Among these, an amino group substituted with a hydrogen atom, an aryl group or a heterocyclic group, and an acylamino group are particularly preferred, and an amino group substituted with an aryl group having a substituent is most preferred.

In the general formula (M-1), R ₁₃ and R ₁₄ are each independently preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, a carbamoyl group, or an alkoxycarbonyl group. Each group may be further substituted.

More specifically, a hydrogen atom, an alkyl group, a cyano group, or a carboxyl group is preferable. Among them, R ₁₃ is preferably a hydrogen atom and R ₁₄ is preferably an alkyl group, and particularly preferably R ₁₃ is a hydrogen atom and R ₁₄ is a methyl group.

  As for the preferred combination of substituents of the compound represented by the general formula (M-1), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

In this invention, the compound represented by the following general formula (M-2) is preferable among the compounds represented by the said general formula (M-1).
General formula (M-2):

一般式（Ｍ−２）中、Ａ、Ｂ₁、Ｂ₂、Ｒ_１１およびＲ_１２は、前記一般式（Ｍ−１）中のＡ、Ｂ₁、Ｂ₂、Ｒ_１１およびＲ_１２と同義である。

In the general formula (M-2), A, B 1, B 2, R 11 and _{R 12,} A in the formula (M-1), at B _1, B _{2, R 11} and _{R 12} as defined is there.

  a and e each independently represents an alkyl group, an alkoxy group or a halogen atom. When a and e are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and May be further substituted.

b, c, and d are each independently synonymous with R ₁₃ and R _{14 in the} general formula (M-1), and a and b or e and d may be condensed with each other. However, General Formula (M-2) has at least one ionic hydrophilic group.

  In this invention, in the said general formula (M-2), A is synonymous with A in the said general formula (M-1), and its preferable example is also the same.

In the present invention, in formula _{(M-2), B 1} , B 2 , the formula (M-1) is _B 1, _{B 2} and synonymous, and preferred examples are also the same.

In the present invention, the general formula _(M-2), R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.

  In the present invention, in the general formula (M-2), a and e each independently represent an alkyl group, an alkoxy group or a halogen atom. When both a and e are alkyl groups, the alkyl group The total number of carbon atoms constituting is 3 or more, and they may be further substituted.

  More preferably, a and e are each independently preferably a methyl group, an ethyl group or an isopropyl group, more preferably an ethyl group or an isopropyl group, and most preferably a = e = ethyl group or isopropyl group.

b, c, and d are each independently synonymous with R ₁₃ and R _{14 in the} general formula (M-1), and a and b or e and d may be condensed with each other. However, General Formula (M-2) has at least one ionic hydrophilic group.

  More preferably, c is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

  b and d are preferably a hydrogen atom or an ionic hydrophilic group. Among them, a hydrogen atom, a sulfo group, or a carboxy group is preferable, and a combination of b and d is most preferably a hydrogen atom and a sulfo group.

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

In this invention, the compound represented by the following general formula (M-3) is preferable among the compounds represented by the said general formula (M-2).
General formula (M-3):

In General Formula (M-3), Z ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ₁₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, a heterocyclic group or an acyl group. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , a, b, c, d, and e have the same meanings as those in the general formula (M-2). Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of the groups Z ₁₁ , Z ₁₂ and Q may further have a substituent. However, General Formula (M-3) has at least one ionic hydrophilic group.

In the present invention, in formula _(M-3), R _{13, R 14,} the formula (M-1) have the same meaning as _{R 13, R 14,} and preferable examples thereof are also the same.

In the present invention, the general formula _(M-3), R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.

  In the present invention, in the general formula (M-3), a, b, c, d and e have the same meanings as a, b, c, d and e in the general formula (M-2), The preferred examples are also the same.

In the present invention, in the general formula (M-3), the electron withdrawing group of Z _{11 is} an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. is there. The upper limit of the σp value is preferably 1.0 or less.

  Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphospho group Group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group Substituted with a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a heterocyclic group, a halogen atom, an azo group, a selenocyanate group, or other electron-withdrawing group having a σp value of 0.20 or more. Aryl group I can get lost.

Z ₁₁ is preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group.

Z ₁₂ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and more preferably an alkyl group. Each substituent may be further substituted.

More specifically, the alkyl group as Z ₁₂ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms.

  Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

  Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl, among which methyl, ethyl, isopropyl T-butyl is preferred, isopropyl and t-butyl are particularly preferred, and t-butyl is most preferred.

The cycloalkyl group as Z ₁₂ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group as Z ₁₂ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.

The aryl group as Z ₁₂ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group as Z ₁₂ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group and 2-furyl group.

The acyl group as Z ₁₂ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

In the present invention, in the general formula (M-3), Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group, or a heterocyclic group. Each of these substituents may be further substituted. Details of these substituents are the same as those of R ₁₃ and R ₁₄ described above.

  Q is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group. The electron-withdrawing group serving as the substituent for Q is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.

Specific examples of the electron-withdrawing group having a σp value of 0.20 or more are the same as Z ₁₁ in the general formula (M-3).

  More specifically, Q is preferably a heterocyclic group substituted with an electron-withdrawing group, and among them, a sulfo group, a substituted or unsubstituted carbamoyl group, a benzoxazole ring substituted with a substituted or unsubstituted sulfamoyl group, benzo A thiazole ring is preferable, and a benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is most preferable.

  As for the preferable combination of substituents of the compound represented by the general formula (M-3), a compound in which at least one of various substituents is the above-described preferable group is preferable, and more various substituents are preferable. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the compound represented by the general formula (M-1) of the present invention includes the following (A) to (D).

(A) Preferred examples of the heterocyclic ring of A include a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, or a benzoisothiazole ring, and further a pyrazole A ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring are preferable, and among them, a pyrazole ring, a triazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring are preferable, and a pyrazole ring is most preferable.

(B) B ₁ and B ₂ each represent -CR ₁₃ = or -CR ₁₄ =, or either one represents a nitrogen atom and the other represents -CR ₁₃ = or -CR ₁₄ =, but B ₁ And B ₂ preferably represents -CR ₁₃ = or -CR ₁₄ =, and R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), R ₁₄ is a hydrogen atom or an alkyl group (B ₂ is unsubstituted) Or a carbon atom substituted with an alkyl group), particularly preferably R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), and R ₁₄ is most preferably a methyl group (a carbon atom in which B ₂ is substituted with a methyl group). .

(C) R ₁₁ and R ₁₂ are each independently a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group A substituted or unsubstituted alkylsulfonyl group and a substituted or unsubstituted arylsulfonyl group, more preferably a hydrogen atom, a substituted aryl group, and a substituted heterocyclic group, and among them, a substituted aryl group and a substituted heterocyclic group are particularly preferable. An aryl group substituted with a sulfo group and a heterocyclic group substituted with a sulfo group are most preferred.

  (D) G is a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, alkyl group or aryl group Or an amino group substituted with a heterocyclic group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, alkyl and arylthio group, heterocyclic thio group Alternatively, an ionic hydrophilic group is preferable, and further, an amino group substituted with a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl group, an aryl group, or a heterocyclic group, an acylamino group Group Preferred, a hydrogen atom, an aryl group or a heterocyclic amino group substituted with groups, particularly preferably an acylamino group, an amino group substituted with an aryl group having a substituent most preferred.

  In the general formula (M-1), the case of the general formula (M-2) is particularly preferable.

  A particularly preferable combination as the compound represented by the general formula (M-2) of the present invention includes the following (A) to (D).

(A) Examples of the heterocycle of A are the same as A in the general formula (M-1), and preferred examples are also the same.

(Ii) _{B 1} and _{B 2} has the same meaning as _{B 1} and _{B 2} in formula (M-1), and preferred examples thereof are also the same.

_(C) R _{11, R 12} has the same meaning as _{R 11, R 12} in formula (M-1), and preferred examples thereof are also the same.

(D) a and e are preferably alkyl groups or halogen atoms. When both a and e are alkyl groups, they are unsubstituted alkyl groups, and the total number of carbon atoms of a and e is 3 or more (preferably 5 or less). A, b, c and d are each a hydrogen atom, a halogen atom, an alkyl group or an ionic hydrophilic group (preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an ionic hydrophilic group). Is preferable. More preferably, a and e are each independently preferably a methyl group, an ethyl group or an isopropyl group, more preferably an ethyl group or an isopropyl group, and most preferably a = e = ethyl group or isopropyl group. Furthermore, c is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group. b and d are preferably a hydrogen atom or an ionic hydrophilic group. Among them, a hydrogen atom, a sulfo group, or a carboxy group is preferable, and a combination of b and d is most preferably a hydrogen atom and a sulfo group.

  In general formula (M-2), the case of general formula (M-3) is particularly preferable.

  A particularly preferable combination as the compound represented by the general formula (M-3) of the present invention includes the following (A) to (F).

(A) Z ₁₁ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less. Z ₁₁ is more preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and most preferably a cyano group.

(B) Z ₁₂ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and more preferably an alkyl group. Each substituent may be further substituted. More specifically, the alkyl group as Z ₁₂ includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Among them, methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl are preferable, isopropyl and t-butyl are particularly preferable, and t-butyl is preferable. Most preferred.

(C) Q represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group. Each of these substituents may be further substituted. Furthermore, Q is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group. The electron-withdrawing group serving as the substituent for Q is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less. More specifically, a heterocyclic group substituted with a Q electron-withdrawing group is preferable, and among them, a benzoxazole ring or a benzothiazole ring substituted with a sulfo group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group. In particular, a benzothiazole ring substituted with a sulfo group or a substituted sulfamoyl group is most preferable.

(D) a, b, c, d and e have the same meanings as a, b, c, d and e in formula (M-2), and preferred examples are also the same.

_{(E) R 13} and _{R 14} has the same meaning as _{R 13} and _{R 14} in the formula (M-2), and preferred examples thereof are also the same.

_(Vi) R _{11, R 12} has the same meaning as _{R 11, R 12} in the above formula (M-2), and preferred examples thereof are also the same.

  The compounds (azo dyes) represented by the general formulas (M-1), (M-2) and (M-3) have at least one ionic hydrophilic group in the molecule (preferably 3 to 6). The following). Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a sulfo group. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Among alkali metal salts, potassium ion, sodium ion and lithium ion are preferable, and lithium ion is most preferable. In particular, from the viewpoint of improving solubility and suppressing bronzing in ink jet printing, a combination of the ionic hydrophilic group being a sulfo group and the counter ion being lithium ion is most preferable.

  The azo dye preferably has 3 or more and 6 or less ionic hydrophilic groups in its molecule, more preferably 3 or more and 6 or less sulfo groups, and 3 or more and 5 or less sulfo groups. More preferably.

  The magenta ink composition of the present invention contains at least one of the compounds represented by the general formulas (M-1), (M-2), and (M-3) and salts thereof as a colorant.

  The ink set of the present invention can include a dark magenta ink composition and a light magenta ink composition as a magenta ink composition. When both the dark magenta ink composition and the light magenta ink composition are included in the ink set, at least one of the two is a colorant containing the dye of the general formula (M-1), (M-2), or (M-3). It is preferable that the light magenta ink composition includes the dye of the general formula (M-1), (M-2), or (M-3) as a colorant. By improving the light resistance and ozone resistance of the light magenta ink composition, the light resistance and ozone resistance of the image of the entire recorded matter can be improved. Most preferably, both the dark magenta ink composition and the light magenta ink composition contain the dyes of the general formulas (M-1), (M-2), and (M-3) as colorants.

  In the ink set of the present invention, the concentration of the dye in the magenta ink composition is appropriately determined based on the color values of the dyes of the general formulas (M-1), (M-2), and (M-3) used. be able to. When only one magenta ink composition is included in the ink set, the total amount of dyes of the general formulas (M-1), (M-2), and (M-3) is generally 2 in the magenta ink composition. It is preferable to contain 0.0-10 mass%. By setting the dye concentration to 2.0% by mass or more, sufficient color developability can be secured as an ink. Further, by setting the dye concentration to 10% by mass or less, the ink composition used in the ink jet recording method can be ejected from a nozzle. It is easy to ensure the property and prevent nozzle clogging.

  When the dark magenta ink composition and the light magenta ink composition are included in the ink set, the dye concentration in the light magenta ink composition is represented by the general formulas (M-1), (M-2), Although it can be appropriately selected according to the color value of the dye of (M-3), in general, in the light magenta ink composition, the general formulas (M-1), (M-2), (M-3) The total amount of the dye is preferably 0.5 to 3.5% by mass, and more preferably 1.0 to 3.0% by mass. By setting the dye concentration to 0.5% by mass or more, the color developability required for the light magenta ink composition can be secured, and by setting the dye concentration to 3.5% by mass or less, the light magenta ink composition can be obtained. It is possible to reduce or prevent graininess in an image of a recorded matter that has been used and recorded.

  When a dark magenta ink composition and a light magenta ink composition are included in the ink set, the content (% by mass) of the colorant contained in the light magenta ink composition and the content of the colorant contained in the dark magenta ink composition The ratio to the amount (mass%) is preferably 1: 2 to 1: 8. By configuring the content of the colorant at such a ratio, the graininess of images recorded using these ink compositions can be reduced. Furthermore, by setting the colorant ratio and the ink composition in which the concentration of the colorant falls within the above range, a good color balance can be realized between the dark magenta ink composition and the light magenta ink composition. It is possible to prevent the inkjet nozzle from being clogged.

  In the ink set of the present invention, it is represented by the general formulas (M-1), (M-2), and (M-3) in the magenta ink composition, the dark magenta ink composition, or the light magenta ink composition. The content of the colorant selected from the group consisting of a compound and a salt thereof depends on the type of each substituent in the general formulas (M-1), (M-2), and (M-3), the type of solvent component, and the like. Ink composition including at least one dye selected from compounds of general formulas (M-1), (M-2) and (M-3) and salts thereof contained in the ink composition The total amount of all colorants contained in the ink composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total mass of the ink composition. . By setting the amount of the colorant in the ink composition to 0.1% by mass or more, color developability or image density on the recording medium can be secured, and by adjusting the amount to 10% by mass or less, the viscosity of the ink composition is adjusted. Therefore, characteristics such as ejection reliability and clogging resistance can be easily secured.

  In addition, examples of magenta dyes used in combination with dyes selected from the group consisting of the compounds represented by the general formulas (M-1), (M-2), and (M-3) and salts thereof include C . I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, C.I. I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. I. Reactive violet 1,3,4,5,6,7,8,9,16,17,22,23,24,26,27,33,34, C.I. I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. I. In addition to basic violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, etc., a coupling component (hereinafter referred to as coupler component) Heteryl or arylazo dyes (hereinafter represented by the general formula (M-11)) having phenols, naphthols, anilines, heterocycles such as pyrazine, open-chain active methylene compounds, etc. Compound); for example, an azomethine dye having an open-chain active methylene compound as a coupler component; an anthrapyridone dye (hereinafter referred to as general formula (M-12) (for example, compound No. 20 in Table 1 described in US2004 / 02393939A1) And compound (13) described in International Publication No. 04/104108 pamphlet) Kill.

The compound represented by the above formula (M-11) is a compound represented by the following general formula (M-11).
General formula (M-11):

[In the formula (M-11), Y represents an alkyl group of C ₁ -C _4, alkoxy group, or OH, SO ₃ H, a phenyl group substituted with COOM, or naphthyl group. Further, B represents H or the following formula.

(Wherein R ¹ represents a C ₁ -C ₄ alkyl group substituted with H, OH, or COOH, and R ² is substituted with OH, OCH ₃ , OC ₂ H ₅ , SO ₃ M, COOM. C ₁ -C ₄ alkyl group, and M represents H, Li, Na, K, ammonium, or organic amines)]

The compound represented by the above formula (M-12) is a compound represented by the following general formula (M-12).
General formula (M-12):

[In the formula (M-12), Z represents a nonmetallic atom group necessary for forming a nitrogen-containing 5- to 6-membered heterocycle. R ₁ , R ₂ , and R ₃ each independently represent a substituent, and these substituents may further have a substituent. m ₁ represents an integer of 0 to 3, m ₂ represents an integer of 0 to 4, and m ₃ represents an integer of 0 to 2, but m ₁ , m ₂ and m ₃ do not represent 0 at the same time. . When m ₁ is 2 or more, the plurality of R ₁ may be the same as or different from each other. When m ₂ is 2 or more, the plurality of R ₂ may be the same or different from each other, and when m ₃ is 2 or more, the plurality of R ₃ may be the same or different from each other. n represents an integer of 1 to 4. When n is 2 or more, the dye mother nucleus may form a dimer, trimer, or tetramer via R ₁ , R ₂ , or R ₃ .

  Hereinafter, the colorant used in the cyan ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the cyan ink composition is not limited to the colorant having a specific structure, but the light resistance and ozone resistance of the ink composition of other colors and the cyan ink composition It is preferable that the difference between light resistance and ozone resistance is small.

In the present invention, the cyan dye used as the colorant in the cyan ink composition is a compound selected from the group consisting of phthalocyanine compounds represented by the following general formula (C-1) and salts thereof.
General formula (C-1):

In the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ or —CO ₂ NV. ₁ V ₂ , —CO ₂ Z, —CO—Z or a sulfo group is represented. Here, each Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro Group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, acyl group, Or represents an ionic hydrophilic group, each Each group may further have a substituent.

a ₁ ~a ₄ and b ₁ ~b ₄ each represent the number of substituents of X ₁ to X ₄ and Y ₁ to Y _4. A _{1 to} a ₄ are each independently an integer of 0 to 4, and all of them are not 0 at the same time. b ₁ ~b ₄ each independently represents an integer of 0-4.

M is a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof. Provided that at least one of X ₁ , X ₂ , X ₃ , X ₄ , Y ₁ , Y ₂ , Y _3, and Y ₄ is an ionic hydrophilic group or a substituent on the ionic hydrophilic group. As a group possessed as )

In the present invention, in the general formula (C-1), a ₁ , a ₂ , a ₃ and a ₄ are 0 or 1, and two or more of a ₁ , a ₂ , a ₃ and a ₄ Is 1, and b ₁ , b ₂ , b ₃ and b ₄ are each preferably an integer such that the sum of a ₁ , a ₂ , a ₃ and a ₄ is 4, respectively.

As described above, in the general formula (C-1), X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NV ₁ V ₂ , It represents any of —CO ₂ NV ₁ V ₂ , —CO ₂ Z, —CO—Z and a sulfo group.

  Z may be the same or different and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl Represents a group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Preferred are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a substituted alkyl is particularly preferable. The group is most preferred.

V ₁ and V ₂ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferred. Most preferred.

Z, V ₁ and V ₂ may further have a substituent, and here, as the substituent which Z, V ₁ and V ₂ may have, independently, a halogen atom (for example, chlorine atom, bromine atom) ); Linear or branched alkyl group having 1 to 12 carbon atoms, aralkyl group having 7 to 18 carbon atoms, alkenyl group having 2 to 12 carbon atoms, linear or branched alkynyl having 2 to 12 carbon atoms Group, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, a cycloalkenyl group having 3 to 12 carbon atoms which may have a side chain (for example, methyl, ethyl , Propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl); aryl groups (eg, phenyl, 4-t-butylphenyl, 2, 4-di-t-amylphenyl); heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); alkyloxy groups (eg methoxy, ethoxy, 2 -Methoxyethoxy, 2-methanesulfonylethoxy); aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl) An acylamino group (eg, acetamide, benzamide, 4- (3-tert-butyl-4-hydroxyphenoxy) butanamide); an alkylamino group (eg, methylamino, butylamino, diethylamino, methylbutylamino); an anilino group (eg, , Phenylamino, 2-chloroanilino; ureido group (eg, phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino group (eg, N, N-dipropylsulfamoylamino); alkylthio group (eg, methylthio) , Octylthio, 2-phenoxyethylthio); arylthio groups (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio); alkyloxycarbonylamino groups (eg, methoxycarbonylamino); sulfones An amide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane); a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl); a sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl); sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); alkyloxycarbonyl group (For example, methoxycarbonyl, butyloxycarbonyl); heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy); azo group (for example, phenylazo, 4-methoxyphenylazo, 4- Pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); acyloxy group (for example, acetoxy); carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy); silyloxy group (Eg trimethylsilyloxy, dibutylmethylsilyloxy); aryloxycarbonylamino group (eg phenoxycarbonylamino); imide group (eg N-succinimide, N-phthalimi); heterocyclic thio group (eg 2-benzothia Zolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio); sulfinyl group (eg 3-phenoxypropylsulfinyl); phosphonyl group (eg phenoxyphosphonyl, octyl) Aryloxycarbonyl group (for example, phenoxycarbonyl); acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl); ionic hydrophilic group (for example, carboxyl group, sulfo group, And 4th grade Moniumu group), cyano groups, hydroxy groups, nitro groups, and amino group.

As the substituted or unsubstituted alkyl group represented by Z, V ₁ and V ₂ , an alkyl group having 1 to 30 carbon atoms is preferable. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in racemic form). Examples of the substituent include the substituents that may be possessed by the general formula I. Among them, the hydroxyl group, ether group, ester group, cyano group, amino group, amide group, and sulfonamide group are associated with the dye. It is particularly preferable because it increases the property and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted cycloalkyl group represented by Z, V ₁ and V ₂ is preferably a cycloalkyl group having 5 to 30 carbon atoms. In particular, the case of having an asymmetric carbon (use in a racemic form) is particularly preferable because of increasing the solubility of the dye and the ink stability. Examples of the substituent include the substituents that the general formula (C-1) may have, among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, and a sulfonamide group. Is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted alkenyl group represented by Z, V ₁ and V ₂ is preferably an alkenyl group having 2 to 30 carbon atoms. In particular, a branched alkenyl group is preferred because it increases the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in a racemic form). Examples of the substituent include the substituents that may be possessed by the general formula I. Among them, the hydroxyl group, ether group, ester group, cyano group, amino group, amide group, and sulfonamide group are associated with the dye. It is particularly preferable because it increases the property and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted alkynyl group represented by Z, V ₁ and V ₂ is preferably an alkynyl group having 2 to 30 carbon atoms. In particular, a branched alkynyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in racemic form). Examples of the substituent include the substituents that the general formula (C-1) may have, among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, and a sulfonamide group. Is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aralkyl group represented by Z, V ₁ and V ₂ is preferably an alkyl group having 7 to 30 carbon atoms. In particular, a branched alkyl group is preferred because of increasing the solubility of the dye and the ink stability, and particularly preferred is a case having an asymmetric carbon (use in racemic form). Examples of the substituent include the substituents that the general formula (C-1) may have, among which a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, and a sulfonamide group. Is particularly preferred because it increases the association of the dye and improves the fastness. In addition, you may have a halogen atom and an ionic hydrophilic group.

The substituted or unsubstituted aryl group represented by Z, V ₁ and V ₂ is preferably an aryl group having 6 to 30 carbon atoms. Examples of the substituent include the substituent that may be possessed by the general formula I. Among them, an electron withdrawing group is particularly preferable because the oxidation potential of the dye is noble and fastness is improved.

The heterocyclic group represented by Z, V ₁ and V ₂ is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle. The heterocyclic groups represented by Z, V ₁ and V ₂ are exemplified below in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited. It is possible to substitute at position 3, 3 and 4. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among them, an aromatic heterocyclic group is preferable, and preferable examples thereof are the same as those described above. Pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole And thiadiazole. They may have a substituent, and examples of the substituent include the substituent that may be contained in the general formula I. Preferred substituents include those of the aryl group, Preferred substituents are the same as the more preferred substituents of the aryl group.

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

  As the number of ionic hydrophilic groups, those having at least two or more in one molecule of the phthalocyanine dye of the present invention are preferable, and those having at least two sulfo groups and / or carboxyl groups are particularly preferable.

Preferred examples of M include hydrogen atoms and metal atoms such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Examples thereof include Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi. Examples of the oxide include VO and GeO. Examples of the hydroxide include Si (OH) ₂ Cr (OH) ₂ and Sn (OH) ₂ . Further, as the _{halides, AlCl, SiCl 2, VCl,} VCl 2, VOCl, FeCl, GaCl, ZrCl , and the like. Of these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.

  In addition, Pc (phthalocyanine ring) may form a dimer (for example, Pc-MLM-Pc) or a trimer via L (a divalent linking group), and M at that time is Each may be the same or different.

The divalent linking group represented by L includes an oxy group —O—, a thio group —S—, a carbonyl group —CO—, a sulfonyl group —SO ₂ —, an imino group —NH—, a methylene group —CH ₂ —, And a group formed by combining them is preferred.

The chemical structure of the phthalocyanine dye of the present invention includes a sulfinyl group (—SO—Z); a sulfonyl group (—SO ₂ —Z); a sulfamoyl group (—SO ₂ NV ₁ V ₂ ); a carbamoyl group (—CONV ₁ V _2). ); An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group (—CO ₂ Z); an acyl group (—CO—Z); an electron-withdrawing group such as a sulfo group, each of the phthalocyanines of the present invention. It is particularly preferable to introduce at least one benzene ring so that the total of the σp values of the substituents of the entire phthalocyanine skeleton is 1.2 or more. Among them, a sulfinyl group (—SO—Z); a sulfonyl group (—SO ₂ —Z); a sulfamoyl group (—SO ₂ NV ₁ V ₂ ) is preferable, and a sulfonyl group (—SO ₂ —Z); a sulfamoyl group ( -SO ₂ NV ₁ V ₂₎ are preferred, a sulfonyl group _(-SO 2 -Z) is most preferred.

  Hammett's substituent constant σp value will be described briefly. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo).

  As for the preferred combination of substituents of the compound represented by the general formula (C-1), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

In the present invention, the cyan dye used as a colorant in the cyan ink composition represented by the general formula (C-1) is preferably composed of a compound represented by the following general formula (C-2) and a salt thereof. It is a compound selected from the group.
General formula (C-2):

In the general formula (C-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, cyclo Alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfo group Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group , Silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino Represents an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. These groups may further have a substituent.

Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.

l, m, n, p, q 1, q 2, q 3, q 4 each independently represents an integer of 1 or 2.

  M is synonymous with the case of general formula (C-1).

  In the present invention, in the general formula (C-2), l, m, n, and p are each independently an integer of 1 or 2, and among them, 2 of l, m, n, and p One or more is preferably 1, and most preferably 1 = m = n = p = 1.

In the general formula (C-2), q ₁ , q ₂ , q ₃ , and q ₄ are each independently an integer of 1 or 2, and among them, q ₁ , q ₂ , q ₃ , and q ₄ Of these, two or more are preferably 2, and most preferably q ₁ = q ₂ = q ₃ = q ₄ = 2.

In the general formula (C-2), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, preferably a substituted or unsubstituted alkyl group, substituted Alternatively, it is an unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a substituted alkyl group is most preferable. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.

In the general formula (C-2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, a halogen atom, an alkyl group, cyclo Alkyl group, alkenyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfo group Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group , Silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino Represents an imido group, a heterocyclic thio group, a phosphoryl group, an acyl group or an ionic hydrophilic group. Among them, hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carbamoyl group, sulfamoyl group, sulfinyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl Group, an acyl group or an ionic hydrophilic group is preferable, and a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a sulfamoyl group, a sulfinyl group, a sulfonyl group and an ionic hydrophilic group are preferable, and a hydrogen atom is particularly preferable.

  In said general formula (C-2), M is synonymous with M in said general formula (C-1), and its preferable example is also the same.

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

In the present invention, the cyan dye used as a colorant in the cyan ink composition represented by the general formula (C-2) is preferably composed of a compound represented by the following general formula (C-3) and a salt thereof. It is a compound selected from the group.
General formula (C-3):

In general formula (C-3), Z ₁ , Z ₂ , Z ₃ , Z ₄ , 1, m, n, p and M are the same as Z ₁ , Z ₂ , Z ₃ , in general formula (C-2), Synonymous with Z ₄ , l, m, n, p and M.

  In the present invention, in the general formula (C-3), l, m, n, and p are each independently an integer of 1 or 2, and among these, 2 of l, m, n, and p One or more is preferably 1, and most preferably 1 = m = n = p = 1.

In the general formula (C-3), Z ₁ , Z ₂ , Z ₃ and Z ₄ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group. An alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, preferably a substituted or unsubstituted alkyl group, substituted Alternatively, it is an unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are preferable, and a substituted alkyl group is most preferable.

More specifically, Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent Z ₁₁ (wherein Z ₁₁ represents — (CH ₂ ) ₃ SO ₃ M ₂ , where M ₂ represents an alkali metal) And / or Z ₁₂ (wherein Z ₁₂ represents — (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH ₃ )), and particularly represented by the general formula (C-3). Preferred is a dye mixture in which the molar ratio of Z ₁₁ and Z ₁₂ contained in the whole cyan dye is Z ₁₁ / Z ₁₂ = 4/0, 3/1, 2/2, 1/3, and among them, Z ₁₁ / _Z 12 = 3/1 as the main component a dye mixture, and or _{Z 11 / Z 12 = 2/} 2 as a main component dye mixtures are most preferred. However, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent.

In — (CH ₂ ) ₃ SO ₃ M ₂ represented by Z ₁₁ , M ₂ is preferably an alkali metal atom, among which lithium, sodium, and potassium ions are preferable, and lithium ion is most preferable.

  In the general formula (C-3), M has the same meaning as M in the general formula (C-2), and preferred examples thereof are also the same.

  As for the preferred combination of substituents of the compound represented by the general formula (C-3), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

In the present invention, the content of the cyan-based dye contained in the cyan ink composition is the type of X ₁ to X ₄ and Y ₁ to Y ₄ in formula (C-1), and to produce the ink composition In the present invention, the total amount of the cyan dye represented by formula (C-1) (the dye of formula (C-1)) is included in the cyan ink composition. The cyan ink composition preferably contains 1 to 10% by mass, more preferably 2 to 6% by mass.

  When the total amount of the dye of the formula (C-1) contained in the cyan ink composition is 1% by mass or more, the color development of the ink on the recording medium when printed can be improved and is required. Image density can be secured. Further, by making the total amount of the dye of the formula (C-1) contained in the cyan ink composition 10% by mass or less, the discharge property of the cyan ink composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  In the ink set of the present invention, a cyan ink composition having a high color density (dark cyan ink composition) and a cyan ink composition having a low color density (light cyan ink composition) are included in the ink set as the cyan ink composition. Can do.

  When the dark cyan ink composition and the light cyan ink composition are included in the ink set of the present invention, at least one of the dark cyan ink composition and the light cyan ink composition is represented by the general formulas (C-1) and (C-2). It is preferable that at least one of the dyes (C-3) is contained as a colorant.

Of the two cyan ink compositions having different color densities, the cyan ink composition having a low color density is at least one selected from the group consisting of the compound represented by formula (C-2) and a salt thereof. Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently Z ₁₁ (wherein Z ₁₁ represents — (CH ₂ ) ₃ SO ₃ M ₂ , where M ₂ represents an alkali metal atom) And / or Z ₁₂ (wherein Z ₁₂ represents — (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH ₃ )), and in particular, the above general formula (C the molar ratio of the _{Z 11} and the _{Z 12} contained in the entire cyan dye represented by -3) _{is, Z 11 / Z 12 = 4} / 0,3 / 1,2 / 2,1 / 3 becomes dye mixture preferably, the main and _{Z 11 / Z 12 = 2/} 2 among them Min become dye mixture being most preferred.

On the other hand, among the two types of cyan ink compositions having different color densities, the cyan ink composition having a low color density is selected from the group consisting of a compound represented by the following general formula (C-4) and a salt thereof. It is also preferable to use at least one compound.
Formula (C-4):

In general formula (C-4), Q _{1 to} Q ₄ , P _{1 to} P ₄ , W _{1 to} W ₄ , and R _{1 to} R ₄ are each independently (= C (J ₁ )-or -N = ), (= C (J ₂ )-or -N =), (= C (J ₃ )-or -N =), (= C (J ₄ )-or -N =). J _{1 to} J ₄ each independently represents a hydrogen atom and / or a substituent. (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ), and at least one of the four rings {ring A: (A), ring B: (B), ring C: (C), ring D: (D)} is a heterocycle .

More specifically, in the cyan ink composition represented by the general formula (C-4), (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), A ring consisting of (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) {A ring: (A), B ring: (B), C ring: (C ) And D ring: (D)}, at least one hetero ring is preferably a nitrogen-containing hetero ring, and among them, the hetero ring is preferably a pyridine ring, a pyrazine ring, a pyrimidine ring or a pyridazine ring. Further, the hetero ring is preferably a pyridine ring or a pyrazine ring, and most preferably a pyridine ring.

More preferably, in the cyan ink composition represented by the general formula (C-4), (Q ₁ , P ₁ , W ₁ , R ₁ ), (Q ₂ , P ₂ , W ₂ , R ₂ ), A ring consisting of (Q ₃ , P ₃ , W ₃ , R ₃ ), (Q ₄ , P ₄ , W ₄ , R ₄ ) {A ring: (A), B ring: (B), C ring: (C ) And D ring: (D)}, and when it represents an aromatic ring, the following general formula (I) is preferred.
Formula (I):

In general formula (I), * represents a bonding position with the phthalocyanine skeleton. G represents —SO—Z ₁ , —SO ₂ —Z ₁ , —SO ₂ NZ ₂ Z ₃ , —CONZ ₂ Z ₃ , —CO ₂ Z ₁ , —COZ ₁ , or a sulfo group. t represents an integer of 1 to 4.

Z ₁ may be the same or different, and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl 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, or a substituted or unsubstituted heterocyclic group;

Preferred Z ₁ in the general formula (I) includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group and a substituted aryl group. Groups are preferred, especially substituted alkyl groups.

Z ₂ and Z ₃ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group Represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.

Preferred examples of Z ₁ and Z ₂ in the general formula (I) include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Among them, a hydrogen atom, a substituted alkyl group, and a substituted aryl group are preferable, and the case where _one of Z ₁ and Z ₂ represents a hydrogen atom and the other represents a substituted alkyl group or a substituted aryl group is most preferable.

In the general formula (I), preferred G is _{-SO-Z 1, -SO 2 -Z} 1, -SO 2 NZ 2 Z 3, -CONZ 2 Z 3, -CO 2 Z 1, include -COZ ₁ Of these, —SO—Z ₁ , —SO ₂ —Z ₁ , and —SO ₂ NZ ₂ Z ₃ are preferred, and —SO ₂ —Z ₁ is most preferred.

  In the above general formula (I), preferable t represents an integer of 1 to 3, among which an integer of 1 to 2 is preferable, and t = 1 is most preferable.

More specifically, in the cyan ink composition represented by the general formula (C-4), when any ring of A ring, B ring, C ring, and D ring is an aromatic ring, at least one It is preferable that an aromatic ring is the following general formula (II).
General formula (II):

  In general formula (II), * represents a bonding position with the phthalocyanine skeleton.

  In the general formula (II), G has the same meaning as the general formula (I), and preferred examples thereof are also the same.

  In the general formula (II), t1 is 1 or 2, and t = 1 is particularly preferable.

  Both the deep cyan ink composition and the light cyan ink composition contain at least one dye of the general formulas (C-1), (C-2), (C-3), and (C-4) as a colorant. It is particularly preferred.

Of the two cyan ink compositions having different color densities, the cyan ink composition having a high color density is at least one selected from the group consisting of the compound represented by formula (C-2) and a salt thereof. In the above, Z ₁ , Z ₂ , Z ₃ , and Z ₄ are each independently a mixture selected from Z ₁₁ or Z ₁₂ and the whole cyan dye represented by the general formula (C-3) the ink set according to claim 10, wherein the molar ratio of _{Z 11} and the _{Z 12,} characterized in that a dye mixture comprising mainly of Z _{11 / Z} 12 = 3/1 is included in.

  As described above, when a dark cyan ink composition and a light cyan ink composition are included in the ink set, the concentration of the colorant in the light cyan ink composition depends on the type of dye used as the colorant. When the composition is combined with the dark cyan ink composition, it can be appropriately determined so as to have a preferable color balance.

  Generally, in the light cyan ink composition, the total amount of the dyes of the general formulas (C-1), (C-2), and (C-3) with respect to the total mass of the light cyan ink composition is 0.00. It is preferable that 4-3.0 mass% is contained. By making the concentration of the colorant in the light cyan ink composition 0.4% by mass or more, the color developability can be made excellent, and the concentration of the colorant is made 3.0% by mass or less. Therefore, it is possible to reduce the graininess of an image recorded using the light cyan ink composition.

  On the other hand, in the dark cyan ink composition, the total amount of the dyes of the general formulas (C-1), (C-2), and (C-3) is 2. It is preferable that 0-10.0 mass% is contained.

  Furthermore, the ratio between the concentration (% by mass) of the colorant contained in the light cyan ink composition and the concentration (% by mass) of the colorant contained in the dark cyan ink composition is 1: 2 to 1: 8. Preferably there is.

  By satisfying such conditions, a good color balance is realized between the light cyan ink composition and the dark cyan ink composition, and the ink jet nozzle can be prevented from being clogged.

As described above, in the cyan ink composition or the dark cyan ink composition and the light cyan ink composition in the ink set of the present invention, a range in which light resistance and ozone resistance are not greatly impaired for the adjustment of the color tone of the ink and the like. For example, other cyan dyes represented by dyes or dye mixtures represented by the following general formula (C-5) can be used in combination.
General formula (C-5)

R ₁ and R ₂ each independently represents a hydrogen atom or a monovalent substituent. The monovalent substituent may further have a substituent. a represents an integer of 0 to 5. b represents an integer of 0 to 5. c represents an integer of 0 to 5.

  Further, other cyan dyes used in the present invention include, for example, C.I. I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251 252, 264, 270, 280, 288, 289, 291, C.I. I. Acid Blue 9,25,40,41,62,72,76,78,80,82,92,106,112,113,120,127: 1,129,138,143,175,181,205,207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, etc. Not.

  Next, the colorant used in the black ink composition constituting the ink set of the present invention will be described.

  In the ink set of the present invention, the colorant used in the black ink composition is not limited to the colorant having a specific structure, but the light resistance and ozone resistance of the ink composition of other colors and the black ink composition It is preferable that the difference between light resistance and ozone resistance is small.

  The ink set of the present invention can be configured to contain a black ink composition as desired.

  By including the black ink composition in the ink set of the present invention, an image having good contrast can be formed on a recording medium.

In the present invention, the black dye used as a colorant in the black ink composition is a compound selected from the group consisting of a compound represented by the following general formula (B-1) and a salt thereof.
General formula (B-1):

In the general formula (B-1), A and B each independently represent an optionally substituted aromatic group or an optionally substituted heterocyclic group (A is a monovalent group, B is a divalent group).
T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =.
V ₁ , R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy Group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or aryl Sulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl and arylthio group, heterocyclic thio group, alkyl and arylsulfonyl group, heterocyclic sulfonyl group, alkyl and arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, or sulfo Represents a group, and each group may be further substituted. R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or An arylsulfonyl group and a sulfamoyl group are represented, and each group may further have a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

  The general formula (B-1) of the present invention will be described in detail.

  In the general formula (B-1) of the present invention, preferable A includes a monovalent aromatic group which may be substituted or a monovalent heterocyclic group which may be substituted. The substituted phenyl group, substituted naphthyl group, substituted or unsubstituted heterocyclic group are preferable. Among them, the phenyl group substituted with the ionic hydrophilic group, the naphthyl group, and the 5- to 6-membered group having a substituent. A nitrogen heterocycle is preferable, and in particular, a phenyl group and a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof) are preferable, and two or more sulfo groups (the salts thereof) are preferable. ), A phenyl group substituted with a carboxyl group (including salts thereof), and a naphthyl group are preferred, and a naphthyl group substituted with 2 or 3 sulfo groups (including salts thereof) is most preferred.

  In the above general formula (B-1), B includes a divalent aromatic group which may be substituted or a divalent heterocyclic group which may be substituted, and more specifically 5 having a substituent. A 6-membered heterocyclic group is preferable, and among them, a 5-membered heterocyclic group having a substituent is preferable. A 5-6 membered heterocycle means a 5-6 membered ring containing a hetero atom. Examples of the hetero atom of the hetero ring include N, S and O atoms.

  The heterocyclic ring represented by B may be condensed with an aliphatic group, an aromatic ring or another heterocyclic ring, and may further have a substituent on the condensed ring. The heterocycle represented by B means both a saturated heterocycle and an unsaturated heterocycle, and preferably an unsaturated heterocycle. In the case of a nitrogen-containing heterocycle, the N atom may be quaternized. Moreover, as for the heterocycle that can be tautomeric, even when only one tautomer is described, other tautomers are also included.

  Particularly preferred examples of the heterocyclic ring represented by B include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a benzothiazole ring, and a thienothiazole ring.

In the general formula (B-1), T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one is a nitrogen atom and the other is = CR ₄₃ -or -CR ₄₄ = However, it is preferable that T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ = from the viewpoint that more excellent performance can be exhibited.

In the general formula (B-1), R ₄₁ and R ₄₂ are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, Represents an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, a sulfamoyl group, and each group may further have a substituent, among which a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group Group, an alkyl or arylsulfonyl group is preferable, and a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group are more preferable, particularly a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, a hydrogen atom, Most preferred is an aryl group having a substituent. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

In the general formula (B-1), preferable V ₁ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, or an aryloxy group. , Heterocyclic oxy group, silyloxy group, acyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryl It represents an oxycarbonylamino group, an alkyl and arylthio group, or a heterocyclic thio group, and each group may be further substituted.

More preferable V ₁ is a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group (an alkylamino group, an arylamino group, a heterocyclic ring). Represents an amino group), and among them, a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferable, and an amino group having a substituent is particularly preferable. An amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  A particularly preferred combination as the compound represented by formula (B-1) of the present invention includes the following (A) to (E).

(A) A is preferably a substituted phenyl group, a substituted naphthyl group, or a substituted or unsubstituted heterocyclic group, and among them, a phenyl group, a naphthyl group, or a substituent substituted with an ionic hydrophilic group. Preferred is a 5- to 6-membered nitrogen-containing heterocycle having a sulfo group (including salts thereof), a phenyl group substituted with a carboxyl group (including salts thereof), or a naphthyl group, and more preferably two or more. Preferred are sulfo groups (including salts thereof), phenyl groups substituted with carboxyl groups (including salts thereof), and naphthyl groups, preferably substituted with 2 or 3 sulfo groups (including salts thereof) A naphthyl group is most preferred.

(B) B is preferably a 5- to 6-membered heterocyclic group having a substituent, and among them, a 5-membered heterocyclic group having a substituent is preferable. Particularly preferred hetero rings include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a benzothiazole ring, and a thienothiazole ring.

(C) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(D) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(E) V ₁ is hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group, hetero A cyclic amino group), and an acylamino group. Among them, a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferable, and an amino group having a substituent is particularly preferable. An amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  As for the preferred combination of substituents of the dye represented by formula (B-1) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (B-2) is preferable among the compounds represented by the said general formula (B-1).
General formula (B-2):

In the general formula (B-2), X represents an N atom or = CW _1- . W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. _{A, V 1, T 1, T 2} , R 41 and _{R 42} is an _A in the general formula (B-1), and _{V 1, T 1, T 2} , R 41 and _{R 42} synonymous. W is synonymous with V ₁ in the general formula (B-1).

  The general formula (B-2) of the present invention will be described in detail.

  In the general formula (B-2) of the present invention, preferable W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, a thiophene ring, an imidazole ring, a thiazole ring). , A benzothiazole ring, a pyridine ring or a pyridazine ring, particularly preferably a substituted phenyl group (particularly a phenyl group substituted at the para position), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

In the general formula (B-2) of the present invention, X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Among them, an electron-withdrawing group having a σp value of 0.30 or more is preferable, an electron-withdrawing group of 0.45 or more is more preferable, and an electron-withdrawing group of 0.60 or more is particularly preferable. It is desirable not to exceed zero. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

  In the said general formula (B-2) of this invention, A is synonymous with A in the said general formula (B-1), and its preferable example is also the same.

In formula (B-2), T ₁ and T ₂ has the same meaning as T ₁ and T ₂ in the general formula (B-1), and preferred examples thereof are also the same.

In the general formula (B-2), R41, R42 has the same meaning as _{R 41, R 42} in the general formula (B-1), it is also preferred examples same.

In formula (B-2), _{V 1} has the same meaning as _{V 1} of the in the general formula (B-1), and preferred examples thereof are also the same.

  A particularly preferable combination as the compound represented by the general formula (B-2) of the present invention includes the following (a) to (f).

(A) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(B) X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(C) A is preferably a substituted phenyl group, a substituted naphthyl group, or a substituted or unsubstituted heterocyclic group, and among them, has a phenyl group substituted with an ionic hydrophilic group, a naphthyl group, and a substituent. A 5- to 6-membered nitrogen-containing heterocycle is preferable, and a phenyl group and a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof) are particularly preferable, and two or more Preferred is a phenyl group or a naphthyl group substituted with a sulfo group (including salts thereof), a carboxyl group (including salts thereof), or a naphthyl substituted with 2 or 3 sulfo groups (including salts thereof) The group is most preferred.

(D) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(E) R ₄₁ and R ₄₂ are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkyl or arylsulfonyl group, more preferably a hydrogen atom, alkyl group, aryl group or heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(F) V ₁ is a hydrogen atom, halogen atom, alkyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, amino group (alkylamino group, arylamino group, hetero A cyclic amino group), and an acylamino group. Among them, a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferable, and an amino group having a substituent is particularly preferable. An amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  As for the preferred combination of substituents of the dye represented by the general formula (B-2) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (B-3) is preferable among the compounds represented by the said general formula (B-2).
General formula (B-3):

In the above general formula (B-3), V ₁ , W, X, T ₁ , T ₂ , R ₄₁ and R ₄₂ are the same as V ₁ , W, X, T ₁ , in the general formula (B-2). the same meaning as T _{2, R 41} and _{R 42.} X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ have the same meaning as V ₁ in the general formula (B-1).

  The general formula (B-3) of the present invention will be described in detail.

In the general formula (B-3) of the present invention, the monovalent group represented by X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a hydrogen atom or a monovalent substitution Represents a group. The monovalent substituent will be described in more detail. 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, a nitro group, an alkoxy group, and an aryl group. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, allylamino group), acylamino group (amide group), aminocarbonylamino Group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl A group, an azo group, or an imide group, each of which may further have a substituent.

Preferred X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amido group, a ureido group Alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof), hydroxyl group (May be a salt), phosphono group (may be a salt) or quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (including salts thereof) , Hydroxyl group (may be a salt), hydrogen atom, sulfo group (including salts thereof), carboxyl group (including salts thereof) In particular, at least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including salts thereof) or a carboxyl group (including salts thereof). It is preferable.

  In the said general formula (B-3), W is synonymous with W in the said general formula (B-2), and its preferable example is also the same.

  In the said general formula (B-3), X is synonymous with X in the said general formula (B-2), and its preferable example is also the same.

In formula (B-3), T ₁ and T ₂ has the same meaning as T ₁ and T ₂ in the general formula (B-2), and preferred examples thereof are also the same.

In formula _{(B-3), R 41} , R 42 has the same meaning as _{R 41, R 42} in the general formula (B-2), and preferred examples thereof are also the same.

In formula (B-3), V1 has the same meaning as _{V 1} of the in the general formula (B-2), it is also preferred examples same.

  A particularly preferred combination as the compound represented by formula (B-3) of the present invention includes the following (a) to (f).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Preferably), a hydroxyl group (including a salt thereof), and a hydrogen atom, a sulfo group (including a salt thereof), and a carboxyl group (including a salt thereof). Preferably, in particular, at least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including salts thereof) or a carboxyl group (including salts thereof). Is preferred.

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) X represents an N atom or ═CW ₁ —, and W ₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(D) T ₁ and T ₂ each represent = CR ₄₃ -and -CR ₄₄ =, or either one represents a nitrogen atom and the other represents = CR ₄₃ -or -CR ₄₄ =, T ₁ and T ₂ are each preferably = CR ₄₃ -and -CR ₄₄ =, respectively, from the viewpoint that more excellent performance can be exhibited.

(E) R ₄₁ and R ₄₂ are preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkyl or arylsulfonyl group, more preferably a hydrogen atom, alkyl group, aryl group or heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(F) V ₁ is a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a silyloxy group, an acyloxy group, an amino group (an alkylamino group, an arylamino group, A heterocyclic amino group), an acylamino group, among which a hydrogen atom, an amino group (including an alkylamino group, an arylamino group, and a heterocyclic amino group) and an acylamino group are preferred, and an amino group having a substituent in particular An amino group substituted with an aryl group having an ionic hydrophilic group as a substituent (such as a substituted anilino group) is most preferable.

  Regarding the preferred combination of substituents of the dye represented by formula (B-3) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In this invention, the compound represented by the following general formula (B-4) and / or (B-5) among the compounds represented by the general formula (B-3) is preferable.
General formula (B-4):

In the general formula _{(B-4), R 43} has the same meaning as _{R 43} in the general formula (B-1). R ₄₄ has the same meaning as _{R 44} in the general formula (B-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (B-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in the above formula (B-3). W is synonymous with W in the general formula (B-3). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.
General formula (B-5):

In the general formula _{(B-5), R 43} has the same meaning as _{R 43} in the general formula (B-1). R ₄₄ has the same meaning as _{R 44} in the general formula (B-1). R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (B-3). R ₄₁ and _{R 42} has the same meaning as _{R 41} and _{R 42} in the above formula (B-3). W is synonymous with W in the general formula (B-3). W ₁₁ has the same meaning as _{W 1} in the general formula (B-2). _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-3), X 2} , X 3, X 4, X 5, X 6 and X ₇ synonymous.

  The general formula (B-4) of the present invention will be described in detail.

In the general formula (B-4) of the present invention, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are X ₁ , X _{2 in the} general formula (B-3). , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ , and preferred examples are also the same.

  In the said general formula (B-4), W is synonymous with W in the said general formula (B-3), and its preferable example is also the same.

In formula _{(B-4), R 41} , R 42 has the same meaning as _{R 41, R 42} in the general formula (B-3), and preferred examples thereof are also the same.

_{R 43, R 44} in the above formula (B-4) has the same meaning as _{R 43, R 44} in the general formula (B-1), and preferred examples thereof are also the same.

In formula _{(B-4), R 45} , R 46 has the same meaning as _{R 41, R 42} in the general formula (B-3), and preferred examples thereof are also the same.

  A particularly preferred combination as the compound represented by formula (B-4) of the present invention includes the following (A) to (E).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Preferably), a hydroxyl group (including a salt thereof), and a hydrogen atom, a sulfo group (including a salt thereof), and a carboxyl group (including a salt thereof). Preferably, in particular, at least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including salts thereof) or a carboxyl group (including salts thereof). Is preferred.

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(D) Preferred examples of R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group, and each group may be further substituted.

More preferred R ₄₃ represents a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, among which a cyano group, A carboxyl group, a carbamoyl group, and an alkoxycarbonyl group are preferable, and a cyano group is particularly preferable.

R ₄₄ is more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an amino group (an alkylamino group, an arylamino group, a heterocyclic amino group). An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, a heterocyclic sulfonylamino group, among which a hydrogen atom, a halogen atom, An alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group are preferable, and a methyl group is particularly preferable.

(E) R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms. R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

  Regarding the preferred combination of substituents of the dye represented by formula (B-4) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

  The general formula (B-5) of the present invention will be described in detail.

In the general formula (B-4) of the present invention, X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are X ₁ , X _{2 in the} general formula (B-3). , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ , and preferred examples are also the same.

  In the said general formula (B-5), W is synonymous with W in the said general formula (B-3), and its preferable example is also the same.

In the general formula (B-5), W ₁₁ has the same meaning as W ₁ in the general formula (B-2), and preferred examples thereof are also the same.

In formula _{(B-5), R 41} , R 42 has the same meaning as _{R 41, R 42} in the general formula (B-3), and preferred examples thereof are also the same.

_{R 43, R 44} in the above formula (B-5) has the same meaning as _{R 43, R 44} in the general formula (B-1), and preferred examples thereof are also the same.

In the general formula (B-5), R ₄₅ and R ₄₆ have the same meanings as R ₄₁ and R _{42 in the} general formula (B-3), and preferred examples are also the same.

  A particularly preferred combination as the compound represented by formula (B-5) of the present invention includes the following (a) to (f).

(A) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an amide group, Ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, alkoxycarbonyl group, sulfo group (including salts thereof), carboxyl group (including salts thereof) A hydroxyl group (which may be a salt), a phosphono group (which may be a salt) or a quaternary ammonium, and among them, a hydrogen atom, a halogen atom, an alkyl group, a sulfo group (including salts thereof), a carboxyl group (a salt thereof) Preferably), a hydroxyl group (including a salt thereof), and a hydrogen atom, a sulfo group (including a salt thereof), and a carboxyl group (including a salt thereof). Preferably, in particular, at least one of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ is a sulfo group (including salts thereof) or a carboxyl group (including salts thereof). Is preferred.

(B) Preferred W is a substituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted heterocyclic group (for example, a pyrrole ring, thiophene ring, imidazole ring, thiazole ring, benzothiazole ring, pyridine ring or pyridazine ring) And particularly preferably a substituted phenyl group (particularly a para-substituted phenyl group), a substituted or unsubstituted β-naphthyl group, a pyridine ring or a thiazole ring.

(C) Preferred W ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Among them, an electron-withdrawing group having a σp value of 0.30 or more is preferable, an electron-withdrawing group of 0.45 or more is more preferable, and an electron-withdrawing group of 0.60 or more is particularly preferable. It is desirable not to exceed zero. More specifically, an acyl group having 2 to 20 carbon atoms, an alkyloxycarbonyl group having 2 to 20 carbon atoms, a nitro group, a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, A carbamoyl group having 1 to 20 carbon atoms and a halogenated alkyl group having 1 to 20 carbon atoms are preferred. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms, and an arylsulfonyl group having 6 to 20 carbon atoms, and most preferred is a cyano group.

(D) R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl or arylsulfonyl group, and more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₁ and R ₄₂ are not simultaneously hydrogen atoms. R ₄₃ and R ₄₁ , or R ₄₁ and R ₄₂ may be bonded to form a 5- to 6-membered ring.

(E) Preferred examples of R ₄₃ and R ₄₄ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heterocyclic group, cyano group, carboxyl group, carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, hydroxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group), acylamino group, ureido group, sulfamoylamino group Represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, or a heterocyclic sulfonylamino group, and each group may be further substituted.

More preferred R ₄₃ represents a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic oxycarbonyl group, among which a cyano group, A carboxyl group, a carbamoyl group, and an alkoxycarbonyl group are preferable, and a cyano group is particularly preferable.

R ₄₄ is more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a hydroxy group, an amino group (an alkylamino group, an arylamino group, a heterocyclic amino group). An acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl or arylsulfonylamino group, a heterocyclic sulfonylamino group, among which a hydrogen atom, a halogen atom, An alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group are preferable, and a methyl group is particularly preferable.

(F) R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkyl group or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, In particular, a hydrogen atom, an aryl group having a substituent, and a heterocyclic group having a substituent are preferable, and an aryl group having a hydrogen atom and a substituent is most preferable. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms. R ₄₅ and R ₄₆ may combine to form a 5- to 6-membered ring.

  Regarding the preferred combination of substituents of the dye represented by formula (B-5) of the present invention, a compound in which at least one of various substituents is the above-described preferred group is preferable, and more various substituents are present. The compound which is the said preferable group is more preferable, and the compound whose all the substituents are the said preferable group is the most preferable.

In the present invention, among the compounds represented by the above general formula (B-4) and / or (B-5), the compounds represented by the following general formula (B-4-I) and / or (B-5-I) are particularly preferable. Is preferable in that it can exhibit more excellent performance.
General formula (B-4-I):

In the general formula (B-4-I), R ₁₁ and R ₁₂ represent an ionic hydrophilic group. Particularly preferred are a sulfo group (including salts thereof) and a carboxyl group (including salts thereof), and among them, a sulfo group is preferred. m and n represent an integer of 1 to 3. Particularly preferably, it represents an integer of 1 to 2, and m = 1 and / or n = 1 is most preferable. W is synonymous with W in the general formula (B-4), and preferred examples are also the same. _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-4), X 2} , X 3, X 4, X 5, X 6 and is synonymous preferred examples and X ₇ are the same.
General formula (B-5-I):

In the general formula (B-4-I), R ₁₁ and R ₁₂ represent an ionic hydrophilic group. Particularly preferred are a sulfo group (including salts thereof) and a carboxyl group (including salts thereof), and among them, a sulfo group is preferred. m and n represent an integer of 1 to 3. Particularly preferably, it represents an integer of 1 to 2, and m = 1 and / or n = 1 is most preferable. W is synonymous with W in the general formula (B-5), and preferred examples are also the same. W ₁₁ is synonymous with W ₁₁ in the general formula (B-5), and preferred examples are also the same. _{X 1, X 2, X 3} , X 4, X 5, X 6 and _{X 7, X} 1 in the general formula _{(B-5), X 2} , X 3, X 4, X 5, X 6 and is synonymous preferred examples and X ₇ are the same.

  Furthermore, in the present invention, at least one selected from the group consisting of dyes of the formula (B-11) is within a range that does not significantly impair light resistance and ozone resistance in order to adjust the color tone of the black ink composition. Dyes and other yellow dyes can also be used in combination.

Examples of the yellow dye used in combination include C.I. I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, C.I. I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195 196, 197, 199, 218, 219, 222, 227, C.I. I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. I. Basic yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40 and the like can be mentioned, but are not limited thereto. .
Formula (B-11);

In the general formula (B-11), G ₁ and G ₂ each independently represent an optionally substituted aryl group or an optionally substituted hetero group, and K represents an arbitrary substituent. L represents a divalent linking group. However, General Formula (B-11) has at least one ionic hydrophilic group.

  Examples of the aryl group include a benzene ring and a naphthalene ring, and examples of the hetero atom of the hetero ring include N, O, and S. The heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. The substituent may be an arylazo group or a heterocyclic azo group.

Furthermore, as the compound (B-11) used in the black ink composition of the invention, a compound represented by the following general formula (B-12) is particularly preferable.
General formula (B-12):

In General Formula (B-12), G ₁ , G ₂ , G ₃ and G ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁ represents a divalent linking group. However, General Formula (B-12) has at least one ionic hydrophilic group.

Further, as the compound (B-12) used in the black ink composition of the invention, a compound represented by the following general formula (B-13) is particularly preferable.
General formula (B-13):

In the general formula (B-13), E ₁ , E ₂ , E ₃ and E ₄ each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. L ₁₁ represents a divalent linking group. However, General Formula (B-13) has at least one ionic hydrophilic group.

Further, as the compound (B-13) used in the black ink composition of the present invention, a compound represented by the following general formula (B-14) is particularly preferable.
General formula (B-14):

In General Formula (B-14), A ring, B ring, and C ring each independently represent an optionally substituted aryl group or an optionally substituted heterocyclic group. A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ each independently represents a hydrogen atom or a substituent. . However, General Formula (B-14) has at least one ionic hydrophilic group. Q ₁ and Q ₂ each independently represent a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group.

  The general formula (B-14) of the present invention will be described in detail.

In the above general formula (B-14) of the present invention, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ , B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ , B ₁₁ , B ₁₂ , B ₁₃ , B ₁₄ , B ₁₅ , B ₁₆ , C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ each independently represent a hydrogen atom or a substituent. Preferred examples of the substituent include an ionic hydrophilic group, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted sulfonylamino group, a substituted or unsubstituted alkyl group, substituted or unsubstituted Substituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted sulfamoyl group, substituted or And an unsubstituted carbamoyl group, among which an ionic hydrophilic group, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl A substituted or unsubstituted sulfamoyl group is preferable, and an ionic hydrophilic group, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted acylamino group, and a substituted or unsubstituted alkyl group are preferable. The group is most preferred.

  The black ink composition of the present invention has the above general formulas (B-1), (B-2), (B-3), (B-4), (B-4-I), (B-5), At least one selected from the dyes of (B-5-I) as a colorant; or the above general formulas (B-1), (B-2), (B-3), (B-4), ( B-4-I), (B-5), at least one selected from the dyes of (B-5-I) and at least one selected from the dyes of the above general formulas (B-11) to (B-14) In addition, the total amount of the colorant is preferably 0.5 to 12% by mass, and 1.0 to 9.0% by mass with respect to the total mass of the black ink composition. More preferably.

  When the total amount of the above-mentioned dyes contained in the black ink composition is 0.5% by mass or more, when an image or the like is recorded on a recording medium using the ink composition, sufficiently good color development and high image density Can be obtained.

  Further, by setting the total amount of the above-mentioned dyes contained in the black ink composition to 12% by mass or less, the viscosity of the ink composition can be adjusted to a preferable value, and the ink composition from the inkjet head can be adjusted. Can be stabilized, and further, clogging of the ink jet head can be prevented.

  Although the colorant used in each ink composition of the present invention and the content of the colorant in the ink composition have been described above, other components contained in each ink composition will be described below.

  Each ink composition in the present invention can be obtained by dissolving the above-described colorant (dye) in an appropriate solvent. As a solvent for dissolving the colorant in each ink composition, water or a mixed liquid of water and a water-soluble organic solvent is preferably used as a main solvent. As water, ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or the like can be used. From the viewpoint of long-term storage, it is preferable to use water that has been subjected to various chemical sterilization treatments such as ultraviolet irradiation and addition of hydrogen peroxide. The water content in each ink composition constituting the ink set of the present invention is preferably 40 to 90% by mass, more preferably 50 to 80% by mass of the ink composition.

  As described above, each ink composition in the present invention can use a water-soluble organic solvent as a solvent together with water. As the water-soluble organic solvent, those having the ability to dissolve the dye are preferable, and those having a vapor pressure smaller than that of pure water are preferable.

  Examples of the water-soluble organic solvent used in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1, Polyhydric alcohols such as 2,6-hexanetriol, diethylene glycol, triethylene glycol and dipropylene glycol, ketones such as acetonylacetone, esters such as γ-butyrolactone and triethyl phosphate, furfuryl alcohol, tetrahydrofurfuryl Although alcohol, thiodiglycol, etc. are preferable, it is not limited to these. By using a water-soluble organic solvent together with water as the solvent of the ink composition, the ejection stability of the ink composition from the ink head can be improved, and the viscosity of the ink composition can be lowered with almost no other change. Etc. can be easily adjusted.

  Further, at least one humectant selected from saccharides can be contained in each ink composition of the present invention. By including a moisturizing agent in the ink composition, when the ink composition is used in the ink jet recording method, it is possible to suppress moisture evaporation from the ink and moisturize the ink. As the saccharide used in the present invention, maltitol, sorbitol, gluconolactone, maltose and the like are preferable. In addition, the water-soluble organic solvent mentioned above may work as a moisturizer.

  The water-soluble organic solvent and / or humectant may be contained in a total amount of 5 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 5 to 20% by mass in the ink composition. By setting these contents to 5% by mass or more, good ink moisture retention can be obtained, and by adjusting the content to 50% by mass or less, the viscosity of the ink composition is adjusted to a preferable viscosity for use in the inkjet recording method. can do.

  Further, a naphthalene aromatic compound having a carboxyl group at the 2-position can be contained in each ink composition of the present invention. Among the naphthalene-based aromatic compounds having a carboxyl group at the 2-position used in the present invention, particularly preferred are alkali metal salts of naphthalene-based aromatic compounds having a carboxyl group at the 2-position. Further, among the alkali metal salts, it is particularly preferable to use a lithium salt. When lithium salt is used, not only the occurrence of the bronze phenomenon can be prevented, but also an effect that clogging of the ink jet nozzle is less likely to occur.

  Examples of the naphthalene-based aromatic compound having a carboxyl group at the 2-position or a salt thereof include 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, and 6-hydroxy-2-naphthoic acid. 4-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 3-methoxy-2-naphthoic acid, 3-ethoxy-2-naphthoic acid, 3-propoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid , 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid, and the like, and salts thereof, particularly lithium salts. Particularly preferred are 2-naphthoic acid and its lithium salt.

  When a salt of a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the ink composition, a method of adding it to the ink in the form of a salt, or a corresponding naphthalene-based aromatic compound having a carboxyl group at the 2-position And any method of adding it and the base which can form a salt separately to an ink composition can be used. Furthermore, in the present invention, at least one selected from the group consisting of a naphthalene-based aromatic compound having a carboxyl group at the 2-position and a salt thereof can be used. Both can be used together.

  The cyan ink composition and / or magenta ink composition of the present invention comprising the above-mentioned group consisting of a naphthalene-based aromatic compound having a carboxyl group at the 2-position and a salt thereof (hereinafter referred to as a naphthalene-based aromatic compound having a carboxyl group at the 2-position) In the case of adding at least one selected from the group consisting of naphthalene-based aromatic compounds having a carboxyl group at the 2-position, 0.1 to 10% by mass is preferably contained in these ink compositions. More preferably, 5-5 mass% is contained. The amount of the naphthalene-based aromatic compound having a carboxyl group at the 2-position contained in the ink composition is the kind of itself, the kind of dye contained in the ink composition, the kind of solvent used in the ink composition, etc. The preferred amount can be determined as appropriate.

  When a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the cyan ink composition, the amount (mass%) of the cyan dye contained in the ink composition and a naphthalene-based aromatic having a carboxyl group at the 2-position It is preferable that ratio (mass%) of group compounds etc. is 1: 0.1 to 1:10, and it is further more preferable that it is 1: 0.3 to 1: 6. When the content of the cyan dye in the cyan ink composition is 1, the occurrence of bronzing can be increased by increasing the content of a naphthalene-based aromatic carboxylic acid having a carboxyl group at the 2-position to more than 0.1. Further, by reducing the content of a naphthalene aromatic compound having a carboxyl group at the 2-position to less than 10, clogging of the ink jet nozzle can be prevented.

  On the other hand, when a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the magenta ink composition, the amount (mass%) of the magenta dye contained in the ink composition and a carboxyl group at the 2-position The ratio of the amount (mass%) of naphthalene-based aromatic compound or the like is preferably 1: 0.5 to 1:10, and more preferably 1: 1 to 1: 6. When the magenta dye content in the magenta ink composition is 1, the content of a naphthalene-based aromatic compound having a carboxyl group at the 2-position is more than 0.5, so that an image in a high humidity environment is obtained. Degradation of image quality due to bleeding can be reduced, and clogging of inkjet nozzles can be prevented by reducing the content of a naphthalene-based aromatic compound having a carboxyl group at the 2-position to less than 10. .

  Other preferable additives to be added to the ink composition constituting the ink set of the present invention will be described below.

  The ink composition constituting the ink set of the present invention preferably contains a nonionic surfactant. By adding a nonionic surfactant, the penetrability of the ink composition into the recording medium is improved, and the ink composition can be quickly fixed on the recording medium during printing. Further, it is preferable that one dot recorded by the ink composition on the recording medium is as close to a perfect circle as possible. However, by containing a nonionic surfactant in the ink composition, an image formed by one dot It is possible to increase the roundness and improve the image quality of the obtained image.

  As a nonionic surfactant used in the present invention, for example, an acetylene glycol surfactant is preferable, but it is not limited thereto. As the acetylene glycol surfactant used in the ink composition of the present invention, in particular, the following general formula (W-1):

(In formula (W-1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a C1-C6 straight chain, cyclic, or branched alkyl chain, and A ₁ O and A ₂ O is each independently a C2-C3 oxyalkylene chain, such as oxyethylene or oxypropylene, or a polyoxyalkylene chain obtained by polymerization or copolymerization of C2-C3 alkylene oxide, such as a polyoxyethylene chain, a polyoxyethylene chain, Represents an oxypropylene chain or a polyoxyethylenepropylene chain, wherein n and m represent A ₁ O or A ₂ O units, that is, the number of repeating oxyalkylenes, and 0 <n <30, 0 <m <30 And a number satisfying 0 <n + m <50). Examples of the acetylene glycol-based surfactant include Surfynol 465 (trademark), Surfynol 104 (trademark) (trade name, manufactured by Air Products and Chemicals Inc.), Olfine PD001 (trademark), Olfine E1010 (trademark). (The above-mentioned trade name, manufactured by Nissin Chemical Industry Co., Ltd.) can be exemplified, and it is preferable to add at least one selected from these to the ink composition constituting the ink set of the present invention.

  In the present invention, the nonionic surfactant is contained in the ink composition so that the nonionic surfactant is preferably contained in the ink composition in an amount of 0.1 to 5% by mass, more preferably 0.5 to 2% by mass. An agent should be added. By containing 0.1% by mass or more of the nonionic surfactant in the ink composition, the permeability of each ink composition with respect to the recording medium can be increased. Further, when the content of the nonionic surfactant in the ink composition is 5% by mass or less, an effect that an image formed with the ink composition on the recording medium is difficult to blur can be obtained.

  Furthermore, in addition to nonionic surfactants, the addition of glycol ethers as penetration enhancers to the ink composition improves the penetrability of the ink composition with respect to the recording medium, and when color printing is performed. At the boundary between adjacent color inks, ink bleeding (bleeding) is reduced, and a very clear image can be obtained. Therefore, it is preferable to add a penetration enhancer to the ink composition constituting the ink set of the present invention.

  The glycol ethers used in the present invention as penetration enhancers include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene Glycol monobutyl ether, triethylene glycol monobutyl ether and the like are preferable, but are not limited thereto. These glycol ethers are preferably contained in the ink composition in an amount of 3 to 30% by mass, more preferably 5 to 15% by mass. By making the addition amount of glycol ethers 3% by mass or more, bleeding (bleeding) between adjacent inks at the time of color printing can be effectively prevented, and further by making this addition amount 30% by mass or less, image It becomes easy to prevent the occurrence of bleeding, and the storage stability of the ink can be improved.

  Further, the ink composition of the present invention includes a pH adjuster such as triethanolamine or alkali metal hydroxide, a water-soluble polymer such as sodium alginate, a water-soluble resin, a fluorosurfactant, an antiseptic, and an antifungal agent. A material selected from a rust inhibitor, a dissolution aid, an antioxidant, an ultraviolet absorber, and the like can be added as desired. These components can be used alone or in combination of two or more. Moreover, it is not necessary to add, if it is not necessary to add. Those skilled in the art can use the preferable additive selected in a preferable amount as long as the effects of the present invention are not impaired. The dissolution aid is an additive for dissolving the insoluble matter and keeping the ink composition in a uniform solution when the insoluble matter is precipitated from the ink composition.

  Examples of the solubilizer include pyrrolidones such as N-methyl-2-pyrrolidone and 2-pyrrolidone, ureas such as urea, thiourea and tetramethylurea, allophanates such as allohanate and methyl allophanate, biuret and dimethylbiuret. And biurets such as tetramethylbiuret can be mentioned, but the invention is not limited to these. Moreover, as an example of the said antioxidant, although L-ascorbic acid and its salt etc. can be illustrated, it is not limited to these.

  Examples of the antiseptic or antifungal agent include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazoline-3. -ON (Avexia Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN (trade name) and the like can be exemplified, but not limited thereto.

  Examples of the pH adjuster include amines such as diethanolamine, triethanolamine, propanolamine, morpholine, and modified products thereof, metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, Examples thereof include ammonium salts such as quaternary ammonium hydroxide (tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate, and other phosphates, but are not limited thereto.

  The ink composition constituting the ink set of the present invention is prepared by including components appropriately selected from the above-mentioned components, but the viscosity of the obtained ink composition is preferably less than 10 mPa · s at 20 ° C. . Furthermore, in the present invention, the surface tension of the ink composition is preferably 45 mN / m or less at 20 ° C., and particularly preferably in the range of 25 to 45 mN / m. By adjusting the viscosity and the surface tension in this manner, an ink composition having desirable characteristics for use in the ink jet recording method can be obtained. The adjustment of the viscosity and the surface tension can be performed by appropriately adjusting and selecting the addition amount of the solvent and various additives to be contained in the ink composition, the kind thereof, and the like.

  The ink composition constituting the ink set of the present invention preferably has a pH of 7.0 to 10.5 at 20 ° C., more preferably 7.5 to 10.0. By making the pH of the ink composition at 20 ° C. 7.0 or more, it is possible to prevent the eutectoid plating of the ink jet head from being peeled off, and to stabilize the ejection characteristics of the ink composition from the ink jet head. Can do. In addition, by setting the pH of the ink composition to 10.5 or less at 20 ° C., it is possible to prevent deterioration of various members that come into contact with the ink composition, for example, members constituting an ink cartridge or an inkjet head. .

  As a method for preparing the ink composition in the present invention, for example, various components contained in the ink composition are sufficiently mixed and dissolved as uniformly as possible, followed by pressure filtration with a membrane filter having a pore size of 0.8 μm, and further. Although the method of preparing the obtained solution by deaeration using a vacuum pump can be illustrated, it is not limited to this.

  Next, the ink set of the present invention using the above-described ink composition can be used as an ink cartridge containing these integrally or independently, and is preferable from the viewpoint of convenient handling. An ink cartridge including an ink set is known in the art, and can be formed into an ink cartridge by appropriately using a known method.

  The ink set or ink cartridge of the present invention can be used for general writing instruments, recorders, pen plotters, and the like, but is particularly preferably used for an ink jet recording method. The ink jet recording method in which the ink set or the ink cartridge of the present invention can be used includes any recording method in which the ink composition is ejected as droplets from a thin nozzle and the droplets are attached to a recording medium. Specific examples of the ink jet recording method in which the ink composition of the present invention can be used will be described below.

  The first method is a method called an electrostatic attraction method. In the electrostatic suction method, a strong electric field is applied between the nozzle and the acceleration electrode arranged in front of the nozzle, and droplet-like ink is continuously ejected from the nozzle, and the ink droplet passes between the deflection electrodes. In the meantime, by supplying a printing information signal to the deflection electrode, the ink droplets are blown toward the recording medium and the ink is fixed on the recording medium, or the image is recorded, or the ink droplets are not deflected, In this method, an image is fixed on a recording medium by ejecting ink droplets from a nozzle onto the recording medium in accordance with a print information signal. The ink set or ink cartridge of the present invention is preferably used in a recording method using this electrostatic suction method.

  The second method is a method for forcibly ejecting ink droplets from the nozzles by applying pressure to the ink liquid with a small pump and mechanically vibrating the ink jet nozzles with a quartz vibrator or the like. The ink droplet ejected from the nozzle is charged at the same time as it is ejected, and while the ink droplet passes between the deflection electrodes, a print information signal is given to the deflection electrode to fly the ink droplet toward the recording medium, This is a method for recording an image on a recording medium. The ink set or ink cartridge of the present invention is preferably used for this recording method.

  The third method is a method in which an image is recorded on a recording medium by simultaneously applying a pressure and a printing information signal to the ink liquid by a piezoelectric element, and ejecting ink droplets from a nozzle toward the recording medium. The ink set or ink cartridge of the present invention is preferably used for this recording method.

  In the fourth method, the ink liquid is heated and foamed using microelectrodes according to the print signal information, and the bubbles are expanded to eject the ink liquid from the nozzle toward the recording medium, thereby forming an image on the recording medium. It is a method of recording. The ink set or ink cartridge of the present invention is preferably used for this recording method.

  The ink set or ink cartridge of the present invention is particularly preferable as an ink composition used when an image is recorded on a recording medium using an image recording method based on an ink jet recording method including the four methods described above. The recorded matter recorded using the ink set of the present invention has excellent image quality and is also excellent in ozone resistance.

  EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

Example 1
After adding deionized water to the following components to make 1 liter, the mixture was stirred for 1 hour while being heated at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and filtered under reduced pressure with a microfilter having an average pore size of 0.25 μm to prepare a yellow ink (Y-1).
Furthermore, the light magenta ink (LM-1), magenta ink (M-1), light cyan ink (LC-1), cyan ink (C-1), black ink ( Bk-1) was prepared, and an ink set 101 having the concentrations shown in Table 1 was prepared.

  PROXEL XL 2 is an Avecia preservative.

Examples 2-8 and Comparative Examples 1-3
In Example 1, ink sets 102 to 111 were prepared by changing the yellow ink (Y-1) to the composition shown in Table 2.

The structure of the dye used above is shown below.
T-1

T-2

T-3 (CI Direct Yellow 132)

T-4

T-5

T-6

T-7 (CI Direct Yellow 86)

  In T-7, M is H.

  A synthesis method of the compound T-4 will be described.

(1) Synthesis of compound b:
25.5 g of sodium hydrogen carbonate and 150 mL of ion-exchanged water were heated to 40 ° C., and 25.0 g of cyanuric chloride (Tokyo Chemicals) was added in 10 divided portions every 10 minutes and stirred for 1 hour. The solution was added dropwise to a mixed solution (8 ° C.) of 52.8 mL of hydrazine and 47 mL of ion exchange water so that the internal temperature did not exceed 10 ° C. The internal temperature was raised to 50 ° C. and stirred for 30 minutes. The precipitated crystals were filtered to obtain 23.4 g of compound b (hydrazine derivative: mp> 300 ° C.). The yield was 94.7%.

(2) Synthesis of compound c:
35.0 g of compound b (hydrazine derivative) was suspended in 420 mL of ethylene glycol and stirred at an internal temperature of 50 ° C. Concentrated hydrochloric acid 59 mL, followed by 60.1 g of pivaloylacetonitrile (Tokyo Chemicals) were added and stirred at 50 ° C. for 10 hours. Concentrated hydrochloric acid (95 mL) and methanol (145 mL) were added, and the mixture was further stirred for 8 hours. After cooling to room temperature, the precipitated crystals were separated by filtration to obtain 81.6 g of compound c (5-aminopyrazole derivative: mp = 233-235 ° C.). The yield was 94.2%. ¹ H-NMR (DMSO-d6), δ value TMS standard: 1.2 to 1.3 (18H, s))

(3) Synthesis of compound e:
90.57 g of compound d (Tokyo Chemicals) was suspended in 500 ml of H ₂ O, and after cooling with 130 ml of concentrated hydrochloric acid, the internal temperature was cooled to 5 ° C. or lower. Next, 36.23 g of sodium nitrite and 70 ml of an aqueous solution were added dropwise at an internal temperature in the range of 4 to 6 ° C., and the mixture was further stirred at an internal temperature of 5 ° C. or lower for 30 minutes. Next, 159 g of sodium sulfite and 636 ml of H ₂ O were injected while maintaining the internal temperature at 20 ° C. or lower, and further 250 ml of concentrated hydrochloric acid was injected at an internal temperature of 25 ° C., followed by stirring at an internal temperature of 90 ° C. for 1 hour. After cooling the internal temperature to room temperature, the mixture was filtered, washed with 200 ml of water and air-dried to obtain 80.0 g of compound e.

(4) Synthesis of compound f:
28 ml of triethylamine was added dropwise at room temperature to 23.3 g of compound e and 209 ml of ethanol suspension, and 12.2 g of ethoxymethylenemalononitrile (ALDRICH product) was added in portions, refluxed for 3 hours, cooled to room temperature, filtered, and 400 ml of isopropyl After washing with alcohol and drying, 23.57 g of compound f was obtained.

(5) Synthesis of T-4:
Acetic acid (145.56 mL) was poured into sulfuric acid (32.4 mL) at an internal temperature of 4 ° C. or lower, and 40% nitrosyl sulfuric acid (15.9 mL) (ALDRICH product) was added dropwise with stirring at an internal temperature of 7 ° C. or lower.
32.4 g of compound f was added in portions and stirred at the same temperature for 60 minutes while stirring at an internal temperature of 10 ° C., and then 1.88 g of compound C in which 1.83 g of urea was added to the reaction mixture was added to 470 ml of methanol. To the suspended solution, a diazonium salt was added dropwise at an internal temperature <0 ° C., and the mixture was stirred as it was for 30 minutes, and then the internal temperature of the reaction solution was raised to room temperature, followed by filtration, methanol washing and H ₂ O washing. Thus, crude crystals were obtained. Subsequently, the crude crystals were suspended in 400 ml of methanol, stirred under reflux for 1 hour, cooled to room temperature, filtered, washed with methanol, washed with water, washed with methanol, dried overnight at 75 ° C., and then free acid form of DYE-11. 34.4 g of crystals were obtained. The obtained crystals were adjusted to 10 wt% aq (at 25 ° C .: pH≈8.3: KOHaq preparation), IPA was added at an internal temperature of 50 ° C., followed by crystallization, cooling, filtration, IPA washing, and drying. 35 g of T-4 was obtained.
_{λmax = 436.4nm (H 2 O)} , ε: 3.53 × 10 4 (dm 3 .cm / mol)

(Evaluation methods)
These ink sets 101 to 111 were packed in a cartridge of an ink jet printer PM820C (manufactured by EPSON), and images were printed on Fuji Photo Film's ink jet paper color photo finishing Pro using the same machine, and the following evaluations were performed.
For image storability, a black print sample was prepared and evaluated as follows.
The light fastness was measured at immediately after printing chromaticity ^{_{(a * 1, b * 1}} ) and lightness _{(L 1)} a Gretag Co. (trade name Spectro Eye), xenon image using weather meter manufactured by Atlas Co. after the light (85,000 lux) was irradiated 14 days, again chromaticity ^{_{(a * 2, b * 2}} ), the brightness determined in accordance with the color of the following (L ₂₎ measured before and after irradiation color difference a (Delta] E) evaluated.
_{^{ΔE = {(a * 1 -a}} * 2) 2 + (b * 1 -b * 2) 2 + (L 1 -L 2) 2} 1/2
For the color difference, the reflection density is evaluated at three points of 1, 1.3, and 1.6. A is the case where the color difference is “5” or less at any density, and B is the case where the reflection point is “5” or more. The density of “5” or more was defined as C.
For gas fastness, the color difference before and after storing the sample for 7 days under an ozone concentration of 5 ppm was evaluated by the same method as for light fastness. Dye residual ratio was evaluated at three points of reflection density of 1, 1.3 and 1.6, and A was given when the color difference was “10” or less at any density, and B was given when “2” was more than “10”. The case where all the concentrations were “10” or more was defined as C. The results are also shown in Table 2.

  From the results in Table 2, it can be seen that each of the ink sets of the Examples has an image with a small change in color tone and is excellent in image preservability as compared with the Comparative Example.

Claims (6)

An ink composition comprising at least one selected from the group consisting of a compound represented by the following general formula (Y-I) and a salt thereof, and CI direct yellow 132 and / or CI direct yellow 86.
Formula (Y-I):

In the formula, G represents a heterocyclic group, and n represents an integer of 1 to 3. When n is 1, R, X, Y, Z, Q, and G represent a monovalent group. When n is 2, R, X, Y, Z, Q, and G each represent a monovalent or divalent substituent, and at least one represents a divalent substituent. When n is 3, R, X, Y, Z, Q, G represents a monovalent, divalent, or trivalent substituent, at least two represent a divalent substituent, or at least one is trivalent. Represents a substituent of   The use ratio of at least one selected from the group consisting of the compound represented by (Y-I) and a salt thereof and CI direct yellow 132 and / or CI direct yellow 86 is 1 as the mass ratio of the former: the latter. The ink composition according to claim 1, wherein the ink composition is from 9 to 9: 1.   An ink set comprising the ink composition according to claim 1.   A recording method comprising applying the ink composition according to claim 1 or 2 onto a recording medium.     A recording method comprising recording by discharging droplets of the ink composition according to claim 1 or 2 onto a recording medium.     A recorded matter recorded using the recording method according to claim 4.