TW201425489A - Ink set, ink cartridge, inkjet printer, inkjet recording method, and recorded matter - Google Patents

Abstract

An ink set, an ink cartridge, an inkjet printer, a recording method, and a recorded matter are provided, wherein the ink set is capable of forming an image having high print density, good color balance, and excellent fading balance because of excellent fastness of ozone gas and light fastness, and the ink set has excellent storage stability. The ink set includes at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition. For example, the black ink composition contains a compound (BLACK-10). For example, a compound (1A) and a compound (2B) are contained as the cyan ink composition.

Description

Ink set, ink cartridge, inkjet printer, inkjet recording method and recorded matter

The present invention relates to an ink set, and particularly relates to an image which is excellent in print density, good color balance, excellent fading balance due to excellent ozone gas fastness and light fastness, and excellent in storage stability. Ink set. Further, the present invention relates to an ink cartridge, an ink jet printer, an ink jet recording method, and a recorded matter using the ink set.

In recent years, the ink jet recording method has been rapidly developed due to its low material cost, high-speed recording, low noise during recording, and easy color recording, and is now being further developed.

In the inkjet recording method, there is a continuous method of continuously flying the droplets, and an on demand method corresponding to the image information signal to fly the droplets, and the ejection method is performed by piezoelectric a method in which a pressure is applied to a droplet to eject a droplet, a method in which a bubble is generated in the ink to eject a droplet by heat, a method of using ultrasonic waves, or an electrostatic force to suck and eject a droplet. The way.

Further, as the ink for inkjet recording, an aqueous ink, an oily ink, or a solid (melt type) ink can be used.

The dye used in the ink for inkjet recording is required to have good solubility in a solvent or dispersibility, and can be recorded at a high concentration, and has a good color, and is active gas (except NOx, light, heat, and environment). In addition to oxidizing gas such as ozone, it is strong in SOx or the like, is excellent in water or chemicals, and has good fixability to a developing material and is not easily bleed out. It is excellent in preservability of ink, non-toxic, and high in purity. Available at low cost.

Recently, a phthalocyanine dye having a specific sulfonyl group or a sulfinyl group is described in Patent Document 2 as a phthalocyanine dye which has a color, a lightness, and an ozone solidity. In addition, in the phthalocyanine dye described in the document, the substitution position as a substituent is compared with the α- and β-position mixed type (when the substitution position of the substituent is irregular), β - a substitution type (when R ₁ to R ₁₆ in the following general formula (IV) are each from 1 to 16 positions, at 2 and/or 3, 6 and/or 7 and 10 And/or 11th, 14th, and/or 15th place having a specific sulfonyl or sulfinyl group) are more excellent in color and light fastness and ozone fastness.

In recent years, a recorded image has been obtained by forming a color image by an inkjet recording method using a plurality of color ink compositions. Generally, the formation of a color image is performed by three colors of a yellow ink composition, a magenta ink composition, and a cyan ink composition, and further, four colors of a black ink composition are added as needed. In addition, six colors of a light cyan ink composition and a light magenta ink composition may be added to the above four colors, or a deep yellow ink set may be further added to the above six colors. The seven colors of the object are formed to form a color image. In this case, two or more ink compositions are combined to form an ink set (see, for example, Patent Document 3 to Patent Document 7).

In the ink set used in the formation of the color image described above, in addition to the requirement that the ink composition of each color has good color rendering properties, it is also required to exhibit a good intermediate color when the ink compositions of the plurality of colors are combined. The obtained recorded matter does not change color during the preservation process. Fading and so on.

In addition, in the ink set, when the specific ink composition is lightfast. Ozone resistance is significantly lower than the light resistance of other ink compositions. In the case of ozone resistance, the color formed by the specific ink composition is discolored and discolored more rapidly than other colors, and the balance of the color tone of the entire image is deteriorated, so that the observer can recognize the ink by the individual. The image formed by the composition fades in a shorter period of time to recognize that the image quality of the image deteriorates.

Therefore, in the ink set, it is preferred to enhance the light resistance of each ink composition constituting the ink set. Ozone resistance, the light resistance of each ink composition. Ozone resistance level, that is, the light of the image formed by each ink composition. The rate of deterioration caused by ozone, such as the fading speed, is also as similar as possible. In other words, it is preferably the light resistance of each ink composition constituting the ink set. Excellent ozone resistance and light resistance between ink compositions. The difference in ozone resistance is small.

Further, regarding the homologous color, the ink set is formed by including two kinds of ink compositions having different color densities, and images of various color densities can be formed, and an image having no graininess can be obtained. This type of ink composition containing two different color concentrations The ink set is mainly used for printing a photographic image, and in order to alleviate or eliminate the graininess of an image when forming a photographic image, an ink composition having a low color density is often used. In addition, in the above light resistance. In the evaluation of ozone resistance, the pattern having an optical density of 1.0 in the evaluation sample was also formed by an ink composition having a low color density. Therefore, in order to improve the lightfastness of the photographic image of the recorded matter. Ozone resistance, and the overall light resistance of the ink set. Ozone resistance, it is important to improve the light resistance of ink compositions with low color density. Ozone resistance.

On the other hand, an ink composition having a rich color density is used for printing of an extremely intense image or a graphic art pattern, and therefore it is also necessary to improve the light resistance of the ink compositions. Ozone resistance.

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-317136

Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-249677

Patent Document 3: Japanese Patent Laid-Open Publication No. 2007-138124

Patent Document 4: Japanese Patent Laid-Open Publication No. 2009-512737

Patent Document 5: Japanese Patent Laid-Open Publication No. 2007-70573

Patent Document 6: Japanese Patent Laid-Open Publication No. 2010-37504

Patent Document 7: Japanese Patent Laid-Open Publication No. 2008-81693

As described above, in the ink set, the light resistance of each ink composition constituting the ink set is desired. Good ozone resistance and light resistance between the ink compositions. The ozone balance is well balanced when exposed to light. The specific color in ozone is no better than its His color fades and/or discolors more quickly. As described above, in the ink set, the performance balance between the ink compositions is important, and therefore, the single and high-performance ink composition is not necessarily suitable for the ink set, and Patent Document 1 to Patent Document 7 cannot be obtained. The desired set of ink sets.

For example, in the α, β-position mixed type of the phthalocyanine dye described in Patent Document 2, the ozone solidity and the printing density do not sufficiently coexist. In the α, β-position hybrid type as described above, by adjusting the substitution position ratio {α bit in the molecule (1 bit, 4 bits, 5 bits, 8 bits, 9 bits, 12 bits, 13 bits, and 16 bits) The β position (2, 3, 6, 7, 10, 11, 14 and 15) is used to control the association, and the balance of the printing concentration and the firmness is obtained. That is, the reason is that the two are in a trade-off relationship, and the performance of the other is not sufficient in order to satisfy one performance.

In addition, in the ink for inkjet recording containing only the β-substituted phthalocyanine dye, the ozone solidity and the printing density are not sufficiently coherent, and there is room for further improvement in the printing density.

Further, in the ink sets described in Patent Document 3 and Patent Document 4, although the light resistance or ozone resistance of each ink composition is improved, the light resistance between the ink compositions is improved. There is room for improvement in the balance of ozone resistance, and further improvement in ink storage stability is required.

Further, Patent Document 6 and Patent Document 7 disclose an ink set in which dyes of respective colors having a specific structure are combined, and although the balance of performance between the ink compositions is emphasized, the balance of light resistance between the ink compositions is not simultaneously satisfied. All the properties of ozone balance, ink storage stability, and any performance requires further Improvement.

Further, in the cyan ink composition, in order to achieve a high printing phase concentration, a triarylmethane-based cyan dye such as Acid Blue is usually used in combination, but the triarylmethane-based dye has a very weak firmness. A disadvantage. Therefore, the fading balance of the cyan dye and the yellow dye and the magenta dye collapses, and especially the ozone fastness of the cyan dye becomes the most important factor determining the chemical reaction speed, so cyan becomes the life of the color image.

The present invention has been made to solve the above problems, and an object of the invention is to provide an image which is excellent in printing density, good in color balance, excellent in fading balance, and excellent in ozone gas fastness and light fastness, and is stable in storage. Excellent ink set. Further, an object of the present invention is to provide an ink cartridge containing the ink set, an ink jet printer featuring the ink cartridge, a recording method using the ink set, and the ink set by the ink set Recorded records.

The inventors of the present invention have found that the dye represented by the formula (1), which is excellent in the association property and has a good printing density, has a combination of the dye represented by the formula (2) which is excellent in association property and excellent in firmness. As a cyan ink, excellent fastness and print density can be coexisted, and by using an ink set using the cyan ink, high print density, good color balance, high level, and excellent fading balance are achieved. Ink set. The means for solving the above problems are as follows.

[1] An ink set comprising at least a black ink composition and a yellow ink composition The composition of the black ink composition and the cyan ink composition, 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 coloring The cyan ink composition contains a phthalocyanine dye represented by the following formula (1) and a phthalocyanine dye represented by the following formula (2) as a colorant.

(In the formula (B-1), A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or -C(R ₂ )= R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may be bonded to each other to form a ring. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent counter cation.

In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime Base, amine methyl methoxy, decyloxy, aryloxycarbonyl, aryloxycarbonylamino, quinone imine, heterocyclic thio, phosphoyl group, sulfhydryl or ionic hydrophilic group . These groups may further have a substituent.

Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, 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 and q ₄ each independently represent 1 or 2.

M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

In the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime A group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group. These groups may further have a substituent.

Z ₅ , Z ₆ , Z ₇ , and Z ₈ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, at least one of Z ₅ , Z ₆ , Z ₇ , and Z ₈ has an ionic hydrophilic group as a substituent.

t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.

M ₂ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

[2] The ink set according to [1], wherein the black ink composition further contains a compound represented by the following formula (B-14).

In the formula (B-14), the A ring, the B ring and the C ring each independently represent a substituted or unsubstituted aryl or 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 and C ₁₄ each independently represent a hydrogen atom or a substituent. Q ₁ and Q ₂ each independently represent a hydrogen atom or a substituent. L ₁₂ represents a divalent linking group. Among them, the compound of the formula (B-14) has at least one ionic hydrophilic group.

[3] The ink set according to [1] or [2], wherein the content of the coloring agent in the black ink composition is 0.1% by mass to 30% by mass based on the total mass in the black ink composition. .

[4] The ink set according to any one of [1] to [3] wherein R ₂ , R ₃ , R ₆ , R ₇ , R in the phthalocyanine dye represented by the general formula (1) ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ are a hydrogen atom.

[5] The ink set according to any one of [1] to [4] wherein R ₁ , R ₄ , R ₅ , R ₈ , R in the phthalocyanine dye represented by the general formula (2) _9. R ₁₂ , R ₁₃ and R ₁₆ are a hydrogen atom.

[6] The ink set according to any one of [1] to [5] wherein Z ₁ , Z ₂ , Z ₃ , and Z ₄ in the phthalocyanine dye represented by the general formula (1) are respectively The substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, or the substituted or unsubstituted heterocyclic group is independently represented.

[7] The ink set according to any one of [1] to [6] wherein Z ₅ , Z ₆ , Z ₇ , and Z ₈ in the phthalocyanine dye represented by the general formula (2) are respectively The substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, or the substituted or unsubstituted heterocyclic group is independently represented.

[8] The ink set according to any one of [1] to [7] wherein Z ₅ , Z ₆ , Z ₇ , and Z ₈ in the phthalocyanine dye represented by the general formula (2) represent In place of the alkyl group, at least one of the substituents of the alkyl group is a -SONHR group (wherein R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group).

[9] The ink set according to any one of [1] to [8] wherein l, m, n and p in the phthalocyanine dye represented by the general formula (1) are 1.

[10] The ink set according to any one of [1] to [9] wherein t, u, v, and w in the phthalocyanine dye represented by the general formula (2) are 1.

[11] The ink set according to any one of [1] to [10] wherein q ₁ , q ₂ , q ₃ and q ₄ in the phthalocyanine dye represented by the general formula (1) are 2 .

[12] The ink set according to any one of [1] to [11] wherein q ₅ , q ₆ , q ₇ and q ₈ in the phthalocyanine dye represented by the general formula (2) are 2 .

[13] The ink set according to any one of [1] to [12] wherein the quality of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) The ratio is 50/50~10/90.

[14] The ink set according to any one of [1] to [13] wherein the content of the phthalocyanine dye represented by the formula (1) in the cyan ink composition is from 0.1% by mass to 10% by mass.

[15] The ink set according to any one of [1] to [14] comprising a compound selected from the group consisting of a compound represented by the following formula (Y), and a formula (Y-2) A yellow ink composition of at least one compound selected from the group consisting of a compound and a salt thereof as a colorant. Among them, the general formula (Y-2) does not contain the general formula (Y).

(In the general formula (Y), M each independently represents a hydrogen atom or a cation, and when M represents a cation, it means a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion or an NH ₄ ⁺ ion)

General formula (Y-2):

In the formula (Y-2), R ₄ represents a monovalent group, R ₅ represents -OR ₆ or -NHR ₇ , R ₆ and R ₇ represent a hydrogen atom or a monovalent group, and X ₃ represents a divalent linking group. , n ₃ is 0 or 1, Ar ₃ represents a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group or a monovalent triazine ring group.

[16] The ink set according to [15], wherein the content of the coloring agent in the yellow ink composition is 1.0% by mass to 6.0% by mass based on the total mass of the yellow ink composition.

[17] The ink set according to any one of [1] to [15] comprising a group selected from the group consisting of a compound represented by the following formula (M-1) and a salt thereof At least one magenta ink composition as a colorant.

In the formula (M-1), A _M represents a 5-membered heterocyclic group.

B ₁ and B ₂ respectively represent -CR ₁₃ =, -CR ₁₄ =, or either B ₁ and B ₂ represent a nitrogen atom, and the other represents -CR ₁₃ = or -CR ₁₄ =.

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an amine. Mercapto, alkylsulfonyl, arylsulfonyl, or aminesulfonyl. Each group may further have a substituent. Wherein R ₁₁ and R _{12 are} not hydrogen atoms at the same time.

G, R ₁₃ and R ₁₄ each independently represent 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 cyano group, a carboxyl group, an aminomethyl group, an alkoxy group. Carbonyl, aryloxycarbonyl, fluorenyl, hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminemethyloxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyl Alkyl, an alkyl group or an aryl or heterocyclic group substituted with an amine group, a mercaptoamine group, a urea group, an aminesulfonyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonyl group Amino or arylsulfonylamino, nitro, alkylthio, arylthio, alkylsulfonyl or arylsulfonyl, alkylsulfinyl or arylsulfinyl, aminesulfonate An anthracenyl group, a heterocyclic thio group, or an ionic hydrophilic group. Each group can be further substituted. Further, R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5-membered ring or a 6-membered ring. Among them, the general formula (M-1) has at least one ionic hydrophilic group.

[18] An ink cartridge comprising the ink set according to any one of [1] to [17].

[19] An ink jet printer loaded with an ink cartridge as described in [18].

[20] An ink jet recording method, characterized in that recording is performed using the ink set according to any one of [1] to [17].

[21] An ink jet recording method, characterized in that an image is formed using the ink set according to any one of [1] to [17].

[22] A recorded matter characterized by using the ink set according to any one of [1] to [17] for recording.

Since the ink set of the present invention uses a specific compound as a coloring agent for the cyan ink composition, the ink storage stability is excellent. The image obtained by using the ink set has a high printing density, a good color balance, and excellent fading balance due to excellent ozone gas firmness and light fastness.

[ink set]

The ink set of the present invention is an ink set including at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition, the black ink composition containing a selected from the following formula (B) -1) expressed At least one of the group consisting of a compound and a salt thereof, the cyan ink dye containing the phthalocyanine dye represented by the following formula (1) and represented by the following formula (2) Phthalocyanine dyes are used as colorants.

(In the formula (B-1), A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or -C(R ₂ )= R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may be bonded to each other to form a ring. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent counter cation)

In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime A group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group. These groups may further have a substituent.

Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, 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 and q ₄ each independently represent 1 or 2.

M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

In the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime A group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group. These groups may further have a substituent.

Z ₅ , Z ₆ , Z ₇ , and Z ₈ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, at least one of Z ₅ , Z ₆ , Z ₇ , and Z ₈ has an ionic hydrophilic group as a substituent.

t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.

M ₂ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

The inventors of the present invention have combined various ink compositions of a plurality of colors to form an ink set for improving ink storage stability and light resistance of the formed image. Ozone resistance research. As a result, it was found that the ink set including the cyan ink composition and the black ink composition using the coloring agent having the specific structure described above is excellent in ink storage stability, and in the case where an image is recorded using the ink set, the printing is performed. High concentration, good color balance, and light fastness of the recorded image. Excellent ozone resistance, and the light of cyan ink and black ink and other color inks. The difference in the speed of deterioration caused by ozone is small, so even due to light. The deterioration of the image caused by ozone progresses to some extent, and an ink set which is difficult for the observer to perceive deterioration of the entire image can be obtained.

Hereinafter, the present invention will be described in detail.

First, in the present invention, the substituent constant σp value of the substituent group A, the substituent group A', the substituent group J, the ionic hydrophilic group, and Hammett is defined.

(substituting group A)

a halogen atom (for example, a chlorine atom or a bromine atom); a linear alkyl group or a branched alkyl group having 1 to 12 carbon atoms; an aralkyl group having 7 to 18 carbon atoms; and an alkenyl group having 2 to 12 carbon atoms; a linear alkynyl group or a branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a side chain, and a cycloolefin having 3 to 12 carbon atoms which may have a side chain a base (as a specific example of the above group, such as methyl, ethyl, propyl, isopropyl, tert-butyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, Cyclopentyl); aryl (eg phenyl, 4-tert-butylphenyl, 2,4-di-t-pentylphenyl); heterocyclyl (eg imidazolyl, pyrazolyl, triazolyl) , 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); alkoxy (eg methoxy, ethoxy, 2-methoxyethoxy, 2 -Methanesulfonyl ethoxy); aryloxy (eg phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-third butyl) Oxylamine, mercaptophenoxy, 3-methoxylamine, mercapto); mercaptoamine (eg, acetamide, benzamide, 4-(3-tert-butyl-4-hydroxybenzene) Oxyphenyl)butanamine); Amino group (for example, methylamino, butylamino, diethylamino, methylbutylamino); anilino (for example, phenylamino, 2-chloroanilino); urea (for example, phenylureido, Methylurea group, N,N-dibutylurea group; amine sulfonylamino group (for example, N,N-dipropylamine sulfonylamino group); alkylthio group (for example, methylthio group, octyl sulfide) Base, 2-phenoxyethylthio); arylthio (eg phenylthio, 2-butoxy-5-th-octylphenylthio, 2-carboxyphenylthio); alkoxycarbonylamine a group (for example, methoxycarbonylamino group); a sulfonamide group (for example, mesylamine, benzenesulfonamide, p-toluenesulfonamide, octadecane); an amine carbenyl group (for example, N-ethylamine A) Sulfhydryl, N,N-dibutylaminecarbamyl); aminoxime (eg N-ethylamine sulfonyl, N,N-dipropylamine sulfonyl, N,N-diethylamine sulfonyl); sulfonyl (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, toluenesulfonyl); alkoxycarbonyl (eg methoxycarbonyl, Butoxycarbonyl); heterocyclic oxy (eg 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); azo (eg phenyl azo, 4-methoxybenzene) Alkyl azo, 4-trimethylethyl decyl phenyl azo, 2-hydroxy-4-propyl phenyl azo azo); an oxiranyloxy group (e.g., ethoxylated); (e.g., N-methylamine methyl methoxy, N-phenylamine methyl methoxy); decyloxy (e.g., trimethyl decyloxy, dibutylmethyl decyloxy); aryloxycarbonylamino ( For example, phenoxycarbonylamino); quinone imine (eg, N-succinimide, N-phthalimin); heterocyclic thio (eg, 2-benzothiazolylthio, 2, 4) - bis-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio); sulfinyl (eg 3-phenoxypropylsulfinyl); phosphinyl (e.g., phenoxyphosphonium, octyloxyphosphonium, phenylphosphonium); aryloxycarbonyl (e.g., phenoxycarbonyl); fluorenyl (e.g., ethyl phenyl, 3-phenylpropyl fluorenyl) Benzyl fluorenyl An ionic hydrophilic group (for example, a carboxyl group, a sulfo group, and a quaternary ammonium group); further, a cyano group, a hydroxyl group, a nitro group, and an amine group.

(substituting group A')

The linear or branched alkyl group having a carbon number of 1 to 12, the linear aralkyl group having a carbon number of 7 to 18 or a branched aralkyl group, and the linear alkenyl group having 2 to 12 carbon atoms may be mentioned. Or a branched alkenyl group, a linear alkynyl group or a branched alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms (for example, methyl group, B group) Base, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl Base, trifluoromethyl, cyclopentyl), halogen atom (eg chlorine atom, bromine atom), aryl group (eg phenyl, 4-tert-butylphenyl, 2,4-di-third Pentylphenyl), heterocyclic (eg imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxy, Nitro, carboxyl, amine, alkoxy (eg methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), aryloxy (eg phenoxy) , 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-tert-butoxycarbonylphenoxy, 3-methoxycarbonylphenoxy), Mercaptoamine (eg, acetamide, benzamide, 4-(3-t-butyl-4-hydroxyphenoxy)butanamine), alkylamine (eg, methylamino, butylamine) , diethylamino, methylbutylamino), arylamine (eg phenylamino, 2-chloroanilino), ureido (eg phenylureido, methylureido, N, N-di Butylureido), sulfonylamino (eg N,N-dipropylamine sulfonylamino), alkylthio (eg methylthio, octylthio, 2-phenoxyethylthio) , an arylthio group (e.g., phenylthio, 2-butoxy-5-th-octylphenylthio, 2-carboxyphenylthio), alkoxycarbonylamino (e.g., methoxycarbonylamino) Alkylsulfonylamine And an arylsulfonylamino group (eg, methylsulfonylamino, phenylsulfonylamino, p-toluenesulfonylamino), an amine carbenyl (eg, N-ethylamine methyl sulfhydryl) , N,N-dibutylaminecarbamyl), amidoxime (eg N-ethylamine sulfonyl, N,N-dipropylamine sulfonyl, N,N-diethylamine sulfonate Sulfhydryl, N-phenylamine sulfonyl), sulfonyl (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), sulfonylamino (eg, A) Sulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane) alkoxycarbonyl (eg methoxycarbonyl, butoxycarbonyl), heterocyclic oxy (eg 1-phenyltetrazole-5) -oxy, 2-tetrahydropyranyloxy), azo (eg phenylazo, 4-methoxyphenylazo, 4-trimethylethenylaminophenyl azo, 2 -hydroxy-4-propylmercaptophenylazo), anthraceneoxy (eg ethoxylated), amine methyloxy (eg N-A) Alkylmethyl methoxy, N-phenylamine methyl methoxy), decyloxy (eg, trimethyl decyloxy, dibutylmethyl decyloxy), aryloxycarbonylamino (eg, phenoxycarbonyl) Amino), quinone imine (eg N-succinimide, N-phthalimin), heterocyclic thio (eg 2-benzothiazolylthio, 2,4-di-phenyloxy) Base-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl (eg 3-phenoxypropylsulfinyl), phosphino group (eg phenoxy) Phosphoninyl, octyloxyphosphonium, phenylphosphonium), aryloxycarbonyl (eg phenoxycarbonyl), fluorenyl (eg ethyl, 3-phenylpropenyl, benzhydryl) ) an ionic hydrophilic group (carboxyl group, sulfo group, quaternary ammonium group, etc.). These substituents may be further substituted, and as a further substituent, a group selected from the substituent group A' described above may be mentioned.

(substituting group J)

For example, a halogen atom, an alkyl 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, an aryloxy group, a decyloxy group, a heterocyclic oxy group , anthraceneoxy, amine methyl methoxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine, decylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonyl Amine, amine sulfonylamino, alkylsulfonylamino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, alkyl sulfin Mercapto or arylsulfinyl, alkylsulfonyl or arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, aminemethantyl, arylazo or heterocyclic azo Examples of the benzylidene group, the phosphinyl group, the phosphino group, the phosphinyl group, the phosphinyloxy group, the phosphinylamino group, the decyl group, and the ionic hydrophilic group are exemplified. These substituents may be further substituted, and as a further substituent, a group selected from the substituent group J described above may be mentioned.

More specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group may, for example, be a linear, branched or cyclic substituted or unsubstituted alkyl group, or a cycloalkyl group or a bicycloalkyl group, or a tricyclic structure having a more cyclic structure. The alkyl group (e.g., alkoxy group, alkylthio group alkyl group) in the substituents described below also represents an alkyl group of this concept. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, and a decyl group. And 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, etc., as a cycloalkyl group, preferably a substituted or unsubstituted cycloalkyl group having a carbon number of 3 to 30, for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group or the like, and a bicycloalkyl group, preferably a substituted or unsubstituted bicycloalkyl group having a carbon number of 5 to 30, that is, a carbon number of 5 A monovalent group obtained by removing one hydrogen atom in the bicycloalkane of ~30, and examples thereof include a bicyclo[1,2,2]heptan-2-yl group and a bicyclo[2,2,2]octane-3-yl group. Wait.

The aralkyl group may, for example, be a substituted or unsubstituted aralkyl group, and a substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenylethyl group are mentioned.

Examples of the alkenyl group include a linear, branched or cyclic substituted or unsubstituted alkenyl group, and a cycloalkenyl group or a bicycloalkenyl group. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group. The base or the like, as the cycloalkenyl group, preferably a substituted or unsubstituted cycloalkenyl group having a carbon number of 3 to 30, that is, a monovalent value obtained by removing a hydrogen atom of a cycloolefin having 3 to 30 carbon atoms. 2-cyclopentyl Examples of the bicycloalkenyl group include a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted carbon number of 5 to 30. a substituted bicycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a bicyclic olefin having one double bond, and, for example, a bicyclo[2,2,1]hept-2-en-1-yl group, Bicyclo[2,2,2]oct-2-en-4-yl and the like.

The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a trimethyldecyl ethynyl group.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, and an o-hexadecanoylamino group. Phenyl and the like.

The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound of 5 or 6 members, more preferably a carbon number. Examples of the aromatic heterocyclic group of 5 or 30 members of 3 to 30 include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group. Octyloxy, 2-methoxyethoxy, and the like.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having a carbon number of 6 to 30, and examples thereof include a phenoxy group, a 2-methylphenoxy group, and a 4-tert-butylphenoxy group. A group, a 3-nitrophenoxy group, a 2-tetradecylaminophenoxy group, and the like.

As the decyloxy group, a substituted or unsubstituted decyloxy group having a carbon number of 0 to 20 is preferable, and examples thereof include a trimethyldecyloxy group and a diphenylmethyl decane group. Oxyl and the like.

The heterocyclic oxy group is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and examples thereof include 1-phenyltetrazole-5-oxyl and 2-tetrahydropyran. Oxyl and the like.

As the decyloxy group, a methyl methoxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having a carbon number of 6 to 30 is preferable. Examples of the oxy group include an ethoxycarbonyl group, a trimethylacetoxy group, a stearyloxy group, a benzamethyleneoxy group, a p-methoxyphenylcarbonyloxy group and the like.

The amine methyl methoxy group, preferably a substituted or unsubstituted amine methyl methoxy group having 1 to 30 carbon atoms, for example, N,N-dimethylamine methyl methoxy group, N, N a diethylamine methyl methoxy group, a morpholinylcarbonyloxy group, an N,N-di-n-octylaminocarbonyloxy group, an N-n-octylamine methyl methoxy group, or the like.

The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, and examples thereof include a methoxycarbonyloxy group and an ethoxycarbonyloxy group. A third butoxycarbonyloxy group, an n-octylcarbonyloxy group or the like.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having a carbon number of 7 to 30, and examples thereof include a phenoxycarbonyloxy group and a p-methoxyphenoxy group. A carbonyloxy group, a p-hexadecyloxyphenoxycarbonyloxy group, or the like.

The amine group includes an alkylamino group, an arylamine group, a heterocyclic amine group, preferably an amine group, a substituted or unsubstituted alkylamino group having a carbon number of 1 to 30, and a carbon number of 6~ Examples of the substituted or unsubstituted anilino group of 30 include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, a triazinylamino group and the like.

As the mercaptoamine group, a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms is preferred. Examples of the carbonylamino group include an ethyl hydrazino group, a trimethyl ethylamino group, a lauryl amine group, a benzhydrylamino group, and a 3,4,5-tri-n-octyloxybenzene group. Alkylcarbonyl group and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, and examples thereof include an amine formamylamino group and an N,N-dimethylaminocarbonyl group. Amino group, N,N-diethylaminocarbonylamino group, morpholinylcarbonylamino group and the like.

The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, and examples thereof include a methoxycarbonylamino group and an ethoxycarbonylamino group. Third butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group and the like.

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, and examples thereof include a phenoxycarbonylamino group and a p-chlorophenoxycarbonylamine. A group, an n-octyloxyphenoxycarbonylamino group, and the like.

The aminesulfonylamino group, preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30, may, for example, be an aminesulfonylamino group or an N,N-dimethylamine. A sulfonylamino group, an N-n-octylaminosulfonylamino group, and the like.

The alkylsulfonylamino group or the arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having a carbon number of 1 to 30 and a carbon number of 6 to 30. Examples of the substituted or unsubstituted arylsulfonylamino group include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, and a 2,3,5-trichloro group. Phenylsulfonylamine Base, p-methylphenylsulfonylamino group and the like.

The alkylthio group is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, and examples thereof include a methylthio group, an ethylthio group, and an n-hexadecanethio group.

The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, and examples thereof include a phenylthio group, a p-chlorophenylthio group, and a m-methoxyphenylthio group.

The heterocyclic thio group is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and examples thereof include a 2-benzothiazolylthio group and a 1-phenyltetrazole-5-yl group. Sulfur-based, etc.

The aminesulfonyl group, preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30, may, for example, be an N-ethylaminesulfonyl group or an N-(3-dodecyloxy group). Propyl sulfonyl, N,N-dimethylamine sulfonyl, N-acetyl sulfonyl sulfonyl, N-benzamide sulfonyl, N-(N'-phenyl Aminomethyl) sulfonyl group and the like.

As the alkylsulfinyl group or the arylsulfinyl group, a substituted or unsubstituted alkylsulfinyl group having a carbon number of 1 to 30, a substituted or unsubstituted carbon number of 6 to 30 is preferable. Examples of the substituted arylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group, and the like.

As the alkylsulfonyl group or the arylsulfonyl group, a substituted or unsubstituted alkylsulfonyl group having a carbon number of 1 to 30, a substituted or unsubstituted carbon number of 6 to 30 is preferable. Examples of the arylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, and a p-methylphenylsulfonyl group.

As a mercapto group, a substituted mercapto group or a substituted or unsubstituted carbon number of 2 to 30 is preferred. a substituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted carbonic acid group bonded to a carbonyl group having 2 to 30 carbon atoms; For example, an ethyl sulfonyl group, a trimethyl ethinyl group, a 2-chloroethyl fluorenyl group, a stearyl group, a benzamyl group, a p-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, and 2- Furanylcarbonyl and the like.

The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, and examples thereof include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, and a m-nitrophenoxy group. A carbonyl group, a p-tert-butylphenoxycarbonyl group, or the like.

The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a third butoxycarbonyl group, and a positive group. Octadecyloxycarbonyl and the like.

As the amine mercapto group, a substituted or unsubstituted oxime group having a carbon number of 1 to 30 is preferable, and examples thereof include an amine methyl sulfonyl group, an N-methyl amine methyl fluorenyl group, and N, N-. Dimethylamine methyl sulfonyl, N,N-di-n-octylamine methyl sulfhydryl, N-(methylsulfonyl)amine carbaryl, and the like.

As the arylazo or heterocyclic azo group, a substituted or unsubstituted arylazo group having a carbon number of 6 to 30, a substituted or unsubstituted carbon number of 3 to 30 is preferable. Examples of the heterocyclic azo group include phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo and the like.

The quinone imine group is preferably an N-succinimide group or an N-phthalimido group.

As the phosphino group, a substituted or unsubstituted carbon number of 0 to 30 is preferred. Examples of the phosphino group include a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group and the like.

The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having a carbon number of 0 to 30, and examples thereof include a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like. .

The phosphinyloxy group is preferably a substituted or unsubstituted phosphinyloxy group having a carbon number of 0 to 30, and examples thereof include a diphenoxyphosphinyloxy group and a dioctyloxyphosphine oxide. Baseoxy and the like.

The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having a carbon number of 0 to 30, and examples thereof include a dimethoxyphosphinylamino group and a dimethylaminophosphine oxide. Amino group.

As the decyl group, a substituted or unsubstituted decyl group having a carbon number of 0 to 30 is preferable, and examples thereof include a trimethyl decyl group, a tert-butyl dimethyl decyl group, and a phenyl dimethyl decane. Base.

(ionic hydrophilic group)

Examples thereof include a sulfo group, a carboxyl group, a thiocarboxy group, a sulfinic acid group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group, and the like. Particularly preferred are a sulfonic acid group and a carboxyl group. Further, the carboxyl group, the phosphonium group and the sulfo group may be in the form of a salt, and examples of the counter cation forming the salt include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion), and an organic cation (for example, tetramethyl group). Ammonium ion, tetramethyl phosphonium ion, tetramethyl phosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a mixed salt containing a lithium salt as a main component, and most preferably Lithium salt.

The counter cation (monovalent counter cation) of the ionic hydrophilic group contained in the compound represented by the formula (B-1) of the present invention preferably contains lithium ions as a main component. The counter cations are not all lithium ions, and the lithium ion concentration in each of the ink compositions is preferably 50% by mass or more, and more preferably 75% by mass or more, based on the entire counter cation in each ink composition. More preferably, it is 80% by mass or more, and particularly preferably 95% by mass or more.

Under the condition of such a ratio, hydrogen ions, alkali metal ions (such as sodium ions, potassium ions), alkaline earth metal ions (such as magnesium ions, calcium ions, etc.), quaternary ammonium ions, and the like may be contained in the ink composition. Grade cesium ions, strontium ions, etc. are used as counter cations.

The types and ratios of the counter-cations of the above-mentioned coloring agents are "New Experimental Chemistry Lecture 9 Analytical Chemistry" (Maruzen, 1977) prepared by the Chemical Society of Japan, and "The 4th Edition Experimental Chemistry Lecture 15 Analysis" prepared by the Chemical Society of Japan ( In 1991, Maruzen) contains a discussion of analytical methods or elements, which can be used to select analytical methods, and to analyze and quantify them. Among them, it is easily determined by an ion chromatography method, an atomic absorption method, or an inductively coupled plasma (ICP) analysis method.

As a method of obtaining the coloring agent of the present invention in which the countercation contains lithium ions, any method can be used. For example, (1) a method of converting a counter cation from another cation into a lithium ion using an ion exchange resin; (2) a method of performing acid precipitation or salting out from a system containing lithium ions; (3) using a counter cation a method for forming a coloring agent by using a raw material of lithium ion and a synthetic intermediate; (4) using a reactant in which a counter cation is a lithium ion, and introducing an ionic progeny by functional group conversion of each coloring agent a method of water-based; (5) a compound in which a counter-cation of an ionic hydrophilic group in a coloring agent is a silver ion, which reacts the compound with a lithium halide solution and removes the precipitated silver halide, thereby making a counter cation A method of turning into lithium ions.

The ionic hydrophilic group in each coloring agent may be any group as long as it is an ionic dissociative group. Preferred examples of the ionic hydrophilic group include a sulfo group (which may also be a salt), a carboxyl group (which may also be a salt), a hydroxyl group (which may also be a salt), a phosphinium group (which may also be a salt), and a quaternary ammonium salt. A sulfhydryl sulfonyl group (which may also be a salt), a sulfhydrylamine carbaryl group (which may also be a salt), a sulfonylamine sulfonyl group (which may also be a salt), and the like.

Preferred are sulfo groups, carboxyl groups or hydroxyl groups (including such salts). When the ionic hydrophilic group is a salt, preferred counter cations include lithium or an alkali metal (for example, sodium, potassium), ammonium, and an organic cation having lithium as a main component (for example, pyridinium, tetramethylammonium, The mixed salt is preferably an alkali metal mixed salt containing lithium or lithium as a main component, and particularly preferably a lithium salt of a sulfo group, a lithium salt of a carboxyl group, or a lithium salt of a hydroxyl group.

(Hamet's substituent constant σp value)

Here, the value of the substituent constant σp of Hammett used in the present specification will be described somewhat. The Hammett's rule is to quantitatively discuss the effects of substituents on the reaction or balance of benzene derivatives, and the rule of thumb advocated by L.P. Hammett in 1935 is widely recognized today. The substituent constants obtained by Hammett's law have σp values and σm values, which can be found in many common books. For example, see "Lange's Handbook of Chemistry" by JADean. 12th edition, 1979 (Mc Graw-Hill) or "Chemical field" supplement, 122, 96-103 pages, 1979 (Nanguangtang). Further, in the present invention, each substituent is limited or described by the substituent constant σp of Hammett, but it is not meant to be limited only to those known in the above-mentioned books. The substituent of the value, of course, also includes a substituent which is included in the range according to the Hammett method even if the value is a value unknown to the literature. The compound represented by the general formula of the present invention is not a benzene derivative, but as a standard for indicating the electronic effect of the substituent, the σp value is used regardless of the position of substitution. In the present invention, the σp value is used in the following sense.

Further, in the present invention, when the compound is a salt, the salt is decomposed into ions in the ink, but is expressed as "containing a salt" for convenience of explanation.

Hereinafter, each ink composition contained in the ink set of the present invention will be described.

First, regarding the coloring agent contained in each ink composition, the ink composition of each color will be described below.

(black ink)

The coloring agent used in the black ink composition constituting the ink set of the present invention will be described.

The black ink composition of the present invention contains at least one compound represented by the following formula (B-1) or a salt thereof which can be used as a black dye as a colorant.

[Dye represented by the general formula (B-1)]

The azo dye used in the ink composition of the present invention is represented by the formula (B-1). In the following, the azo dye (black dye) represented by the formula (B-1) (hereinafter sometimes referred to as "the azo compound represented by the formula (B-1)", "azo dye" Or "water-soluble dyes").

(In the formula (B-1), A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. G represents a nitrogen atom or -C(R ₂ )= R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ may be bonded to each other to form a ring. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent counter cation)

G in the formula (B-1) represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group, and examples of the substituent when the amine ondenyl group has a substituent include an alkyl group (methyl group, ethyl group B). Base), aryl (phenyl).

Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. At least one of Y ₂ , Y ₃ and Y ₄ represents a substituent. The substituent group in the case where Y ₂ , Y ₃ and Y ₄ represent a substituent may independently be the above-mentioned substituent group J.

In the formula (B-1), Y ₂ , Y ₃ and Y _{4 are} preferably each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted amino group, substituted or unsubstituted. Aminomethyl, substituted or unsubstituted sulfonyl, substituted or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino, substituted Or any of the unsubstituted mercaptoamine groups. When Y ₂ , Y ₃ and Y ₄ are a substituted or unsubstituted amino group, a heterocyclic amino group is preferred.

More preferably, Y ₂ , Y ₃ and Y ₄ are each independently a hydrogen atom, an ionic hydrophilic group, a substituted or unsubstituted heterocyclic amine group, a substituted or unsubstituted alkylsulfonylamino group. Any one of a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted mercaptoamine group, and Y ₂ , Y ₃ and Y ₄ are each preferably independently a hydrogen atom, Any of substituted or unsubstituted heterocyclic amine groups, substituted or unsubstituted arylsulfonylamino groups, substituted or unsubstituted decylamino groups.

The substituents when the heterocyclic amine group, the amine sulfonyl group, the alkylsulfonylamino group, the arylsulfonylamino group, and the mercaptoamine group represented by Y ₂ , Y ₃ and Y ₄ have a substituent, More preferably, they are each independently an ionic hydrophilic group (for example, -CO ₂ M, -SO ₃ M: M is a monovalent counter cation).

Y ₂ , Y ₃ and Y ₄ may further have a substituent. Examples of the further substituent include a hydroxyl group, a substituted or unsubstituted amine group or an aryl group which may have an ionic hydrophilic group, and may have an ionic hydrophilic group. The heterocyclic group of the group is preferably a substituted or unsubstituted amine group. As the substituent of the substituted amino group, for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and more preferably an ionic group are preferable. A hydrophilic group-substituted alkyl group or an aryl group substituted with an ionic hydrophilic group.

As the heterocyclic amine group, a substituted or unsubstituted triazinylamino group is preferred, and a triazinylamino group having a substituent is more preferred.

The substituent which the triazinylamino group has is preferably a substituted or unsubstituted amino group, particularly preferably a substituted or unsubstituted amine group.

As the substituent of the substituted amino group, the above examples can be suitably used. Here, the alkyl group in the alkyl group substituted with an ionic hydrophilic group is preferably a methyl group, an ethyl group or a n-propyl group, and more preferably an ethyl group. The aryl group in the aryl group substituted with an ionic hydrophilic group is preferably a phenyl group.

The mercaptoamine group is preferably an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group or a n-propyl group, more preferably an ethyl group. As the aryl group in the arylcarbonylfluorenyl group, a phenyl group is preferred.

Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. Y ₂ , Y ₃ and Y ₄ may be bonded to each other to form a ring, and examples of the ring formed by bonding Y ₂ , Y ₃ and Y _{4 to} each other include a benzene ring and a naphthalene ring, and a benzene ring is preferred.

Y _2, Y ₃ and Y ₄ being, preferably Y ₃ represents a substituent group, more preferably Y _2, and Y ₄ represents a hydrogen atom, Y ₃ represents a substituent.

In particular, it is preferable that Y ₂ and Y ₄ represent a hydrogen atom, and Y ₃ is a heterocyclic amine group having a substituted or unsubstituted amino group as a substituent, and an aryl sulfonate having an ionic hydrophilic group as a substituent. A mercaptoamine group or a mercaptoamine group having an ionic hydrophilic group as a substituent.

Specific examples of the substituent of Y ₂ , Y ₃ and Y ₄ include the following substituents (A1).

(In the substituent (A1), * represents a bonding bond as Y ₂ to Y ₄ . L ₁ represents a single bond, a carbonyl group, or a sulfonyl group. R ₁ represents a substituted or unsubstituted alkyl group, substituted or not Substituted aryl, substituted or unsubstituted heterocyclic group)

R _{1 is} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a substituent having a substituent may be an ionic hydrophilic group. An arylamine group or an alkylamino group.

The above substituent (A1) is preferably the following substituent (A2) or substituent (A3).

(In the substituent (A2) and the substituent (A3), * represents a bond to Y ₂ to Y ₄ . L ₂ represents a carbonyl group or a sulfonyl group. R _A2 represents a substituted or unsubstituted alkyl group, Or a substituted or unsubstituted aryl group. R _A3 represents a substituted or unsubstituted heterocyclic group)

R _A2 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, preferably an alkyl group. The substituent in the case of having a substituent is preferably an ionic hydrophilic group.

L _{2 is} preferably a carbonyl group.

R _A3 represents a substituted or unsubstituted heterocyclic group, and the substituent having a substituent is preferably an alkylamino group or an arylamine group, more preferably an alkylamino group or an arylamino group, and these groups are preferred. It may further have a substituent and is preferably substituted by an ionic hydrophilic group.

The above substituent (A3) is preferably the following substituent (A4).

(In the substituent (A4), * represents a bonding bond as Y ₂ to Y ₄ . R _A4 each independently represents a substituted or unsubstituted alkylamino group, or a substituted or unsubstituted arylamine. base)

R _A4 each independently represents a substituted or unsubstituted alkylamino group or a substituted or unsubstituted arylamine group, and the substituent having a substituent is preferably an ionic hydrophilic group.

Specific examples of the alkyl group, the aryl group, the heterocyclic alkylamino group, the arylamine group, and the ionic hydrophilic group in the above substituent (A1) to the substituent (A4), and Y ₂ , Y ₃ and Y The specific examples in ₄ are the same.

Specific examples of the substituent (A1) to the substituent (A4) are shown below, but are not limited to the following examples. * indicates a bond key as Y ₂ ~ Y ₄ .

A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. As the aryl group, a substituted or unsubstituted aryl group is included. More specifically, an aryl group having a substituent group J can be mentioned.

The aryl group represented by A is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted phenyl group. Examples of the substituent include the group described in the above-mentioned substituent group J, and it is preferred that the ionic hydrophilic group or the Hammett has a σp value of 0.3 or more.

The nitrogen-containing heterocyclic group represented by A includes a substituted or unsubstituted nitrogen-containing heterocyclic group. As the heterocyclic group represented by A, it is preferably substituted or not taken from 5 members. The monovalent group obtained by removing one hydrogen atom from the substituted aromatic or non-aromatic heterocyclic compound is more preferably a 5-membered aromatic heterocyclic group having 2 to 4 carbon atoms. Examples of the substituent include the groups described in the above-mentioned substituent group J. The nitrogen-containing 5-membered heterocyclic group is represented by a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring or a thiadiazole ring, unless the substitution position is defined.

A is preferably an aryl group having a substituent, more preferably an aryl group having an ionic hydrophilic group or a Hammett's σp value of 0.3 or more, and more preferably an ionic hydrophilic group or a ha Mitt has a σp value of 0.3 or more electron withdrawing phenyl groups.

The ionic hydrophilic group in the formula (B-1) is preferably -SO ₃ M ₁ or -CO ₂ M ₁ , more preferably -SO ₃ M ₁ , particularly preferably -SO ₃ Li.

The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include ammonium ion, alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic cation ( For example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium). As the counter cation other than lithium ion, potassium ion and sodium ion are preferable, and sodium ion is more preferable.

The salt to be formed is preferably a lithium salt, a sodium salt, a potassium salt or an ammonium salt, more preferably a lithium salt or a mixed salt containing a lithium salt as a main component, and most preferably a lithium salt.

When the azo compound represented by the formula (B-1) is a mixed salt, lithium is preferred from the viewpoints of solubility in water, viscosity of an aqueous solution, surface tension, and storage stability of a high-concentration aqueous solution. A mixed salt of a salt and a sodium salt may represent a lithium ion in a part of a plurality of M, and the remaining M represents a form of a sodium ion, and may also be a dye in which all M in the formula (B-1) represents a lithium ion. All M in formula (B-1) means sodium The form of ionic dye mixing.

When M is a mixed salt of a lithium salt and a sodium salt, the molar ratio (Li:Na) of the lithium salt to the sodium salt is preferably 99:1 to 25:75, particularly preferably 99:1 to 50:50, more preferably Jia is 99:1~55:45, among which, the best is 99:1~65:35. If it is this range, there is solubility in water. The dissolution rate is good, and the viscosity and surface tension of the high-concentration aqueous solution are easily adjusted, and the storage stability of the high-concentration aqueous solution tends to be excellent. Therefore, for example, a water-soluble ink composition, particularly a water-soluble ink for inkjet, is obtained. It is easy to formulate the constituent elements of the ink composition, and it is possible to provide an excellent raw material (high-concentration aqueous solution, ink composition) which satisfies the required performance of the water-soluble ink for inkjet at a high level.

The ratio of the cations of the mixed salt can be determined by ion chromatography analysis.

The combination which is particularly preferable as the compound represented by the formula (B-1) is the following (i) to (v).

(i) G represents a nitrogen atom or -C(R ₂ )=, preferably -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine mercapto group, or a cyano group, preferably an aminomethyl group (-CONH ₂ group) or a cyano group, more preferably a cyano group.

(ii) A is preferably an aryl group having a substituent, more preferably an aryl group having an ionic hydrophilic group or a Hammett having a σp value of 0.3 or more, and more preferably having 2 ionicities. A hydrophilic group of phenyl groups.

(iii) Y ₂ , Y ₃ and Y _{4 are} preferably independently a hydrogen atom, a substituted or unsubstituted heterocyclic amine group, an ionic hydrophilic group, a substituted or unsubstituted amine methyl fluorenyl group. , substituted or unsubstituted sulfonyl, substituted or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino, substituted or unsubstituted Any of a mercaptoamine group, more preferably a hydrogen atom, a heterocyclic amine group having a substituted or unsubstituted amino group as a substituent, an ionic hydrophilic group, a substituted or unsubstituted alkyl sulfonate Any of a mercaptoamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted mercaptoamine group, particularly preferably a hydrogen atom, having a substituted or unsubstituted Any one of a heterocyclic amine group having a substituent as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, and a mercaptoamine group having an ionic hydrophilic group as a substituent. The mercaptoamine group is preferably an alkylcarbonylfluorenyl group, an alkylcarbonylfluorenyl group having an ionic hydrophilic group as a substituent, and an arylcarbonylfluorenyl group having an ionic hydrophilic group as a substituent. The alkyl group in the alkylcarbonylcarbonyl group is preferably a methyl group, an ethyl group or a n-propyl group, more preferably an ethyl group. As the aryl group in the arylcarbonylfluorenyl group, a phenyl group is preferred.

Most preferably, Y ₂ and Y ₄ represent a hydrogen atom, and Y ₃ is a heterocyclic amine group having a substituted or unsubstituted amino group as a substituent, and an arylsulfonyl group having an ionic hydrophilic group as a substituent. An amine group or a mercaptoamine group having an ionic hydrophilic group as a substituent.

(iv) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, and -SO ₃ M ₁ is more preferred, and -SO ₃ Li is particularly preferred.

(v) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (e.g., lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

As a preferred factor for the structure, the water solubility of the azo compound of the formula (B-1) can be increased, and it can be electronically. An azo dye structure capable of coexisting with good color, coloring power, and high storage stability is provided three-dimensionally.

As a result, the storage stability of the ink composition is improved, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, and thus A preferred example.

The compound represented by the above formula (B-1) is preferably a compound represented by the following formula (2-1).

Hereinafter, the compound represented by the formula (2-1) or a salt thereof will be described in detail.

(In the formula (2-1), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5 member. Heterocyclic group. M independently represents a hydrogen atom or a monovalent counter cation)

Formula (2-1) in the G, A, examples of R ₂ and M are each independently an example in the general formula (B-1) of G, A, R ₂ and M are the same meaning as the preferred embodiment The same is true.

As the monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ in the formula (2-1), the substituent group A' may be independently listed, preferably substituted or not. The substituted alkyl group, the substituted or unsubstituted aryl group, the substituted or unsubstituted heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group (for example, an alkyl group having 1 to 10 carbon atoms) Base, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, or tert-butyl, more preferably methyl, ethyl, or n-propyl Further, the group is more preferably n-propyl) or an aryl group substituted with an ionic hydrophilic group (exemplified by an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, more preferably a phenyl group). .

The compound represented by the above formula (B-1) and formula (2-1) is preferably a compound represented by the following formula (3-1).

Hereinafter, the compound represented by the formula (3-1) or a salt thereof will be described in detail.

General formula (3-1)

(In the formula (3-1), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a a valence substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and M in the formula (3-1) are independently and G, R ₂ and R ₁₁ in the above formula (2-1), respectively. Examples of R ₁₂ , R ₁₃ , R ₁₄ and M have the same meanings, and preferred examples are also the same.

In the formula (3-1), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ and X ₅ represent a substituent include the above-mentioned substituent group J.

X ₁ , X ₂ , X ₃ , X ₄ , and X _{5 are} preferably independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, substituted or Unsubstituted arylsulfonyl, nitro, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted aminyl, substituted or unsubstituted sulfonamide, Preferably, it is a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group, a nitro group, a methoxycarbonyl group, an amine carbenyl group, particularly preferably a hydrogen atom, an ionic hydrophilic group, Or cyano.

In the formula (3-1), X ₂ and X ₄ are each preferably independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X _{5 are} preferably each independently a hydrogen atom or a substituent group J, and more preferably at least one of X ₁ , X ₃ , and X ₅ represents a σp value of Hammett. It is a pull electron base of 0.3 or more. The upper limit of the substituent constant σp value of Hammett is 1.0 or less.

If at least one of X ₁ , X ₃ , and X ₅ is a zeta electron group having a σp value in the range, the color of the azo compound can be adjusted, and the light fastness and the ozone gas firmness can be improved, and it can be used as an inkjet recording black. The ink can obtain an effect from the viewpoint of a water-soluble dye.

Specific examples of the electron withdrawing group having a σp value of 0.3 or more include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphine oxime. , diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfonylthio Aminesulfonyl, thiocyanate, thiocarbonyl, alkyl halide, halogenated alkoxy, halogenated aryloxy, halogenated alkylamino, halogenated alkylthio, other electrons with a σp value of 0.3 or more A substituted aryl, nitro, heterocyclic, halogen atom, azo group, or selenocyanate group. Preferred is a cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, an amine carbenyl group, a nitro group, more preferably a cyano group, a methylsulfonyl group or a nitro group.

In view of the color, the coloring power, and the water-soluble storage stability, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and preferably X ₁ , X ₃ , And X ₅ is a hydrogen atom or a Hammett having a σp value of 0.3 or more, more preferably X ₁ , X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic hydrophilic groups. As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -CO ₂ M ₁ , particularly preferably -CO ₂ Li.

The combination which is particularly preferable as the compound represented by the formula (3-1) is the following (i) to (v).

(i) X ₂ and X ₄ are each preferably independently a hydrogen atom or an ionic hydrophilic group, and at least one of X ₁ , X ₃ and X ₅ preferably represents a Hammert σp value of 0.3 or more. Electron-based, cyano, methylsulfonyl, phenylsulfonyl, methoxycarbonyl, aminecaraki, nitro, more preferably cyano, methylsulfonyl, nitro, and thus more preferably It is a cyano group, particularly preferably X ₁ , X ₂ , X ₃ and X ₄ are a hydrogen atom, and X ₅ is a cyano group.

(ii) G represents a nitrogen atom or -C(R ₂ )=, preferably -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine mercapto group, or a cyano group, preferably an aminomethyl group (-CONH ₂ group) or a cyano group, more preferably a cyano group.

(iii) The monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may, for example, be a substituted group A', preferably a substituted or unsubstituted alkyl group, substituted or unsubstituted The substituted aryl group, the substituted or unsubstituted heterocyclic group is more preferably an alkyl group substituted with an ionic hydrophilic group or an aryl group substituted with an ionic hydrophilic group.

(iv) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, and -SO ₃ M ₁ is more preferred, and -SO ₃ Li is particularly preferred.

(v) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (e.g., lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

As a preferable factor of the structure, the water solubility of the azo compound of the formula (3-1) and the association of the azo dye in the ink composition are remarkably improved, and in particular, the storage in the ink composition is stable. Sexual improvement.

As a result, it can be stably stored for a long period of time, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, which is a preferred example.

The compound represented by the above formula (B-1), formula (2-1) or formula (3-1) is preferably a compound represented by the following formula (4-1).

Hereinafter, the compound represented by the formula (4-1) or a salt thereof will be described in detail.

(In the formula (4-1), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ independently represents a hydrogen atom or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and M in the formula (4-1) are independently and independently R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ in the above formula (2-1). The examples of M have the same meaning, and the preferred examples are also the same.

Examples of X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ in the formula (4-1) are independently the same as X ₁ , X ₂ , X ₃ , and X in the above formula (3-1). The examples of ₄ and X _{5 have} the same meaning, and the preferred examples are also the same.

The reason why the structure is preferable is as follows: the ring containing G in the formula (B-1) is not a nitrogen-containing 5-membered heterocyclic ring and becomes a thiophene ring, and the ink composition of the present invention can be improved at a higher level. The image retention of the object is preserved (eg, ozone gas firmness, light fastness), discoloration (color change), fading (decoloration), and discoloration is required. The gray ink with little change in fading is more adaptable to black ink.

The compound represented by the above formula (B-1), formula (2-1), formula (3-1) or formula (4-1) is preferably represented by the following formula (5). compound of.

Hereinafter, the compound represented by the formula (5) or a salt thereof will be described in detail.

General formula (5)

(In the formula (5), M ₁ , M ₂ , M ₃ , M ₄ and M ₅ each independently represent a hydrogen atom or a monovalent counter cation, when M ₁ , M ₂ , M ₃ , M ₄ , and When M ₅ represents a monovalent counter cation, it means lithium ion, sodium ion, potassium ion, or ammonium ion)

The compound represented by the above formula (B-1) is preferably a compound represented by the following formula (2-2).

Hereinafter, the compound represented by the formula (2-2) or a salt thereof will be described in detail.

(In the formula (2-2), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. R ₃ represents a monovalent substituent. A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group. M independently represents a hydrogen atom or a monovalent counter cation. )

General formula (2-2) is A, G, M, and examples of R ₂ are independently an example in the general formula (B-1) of A, G, R ₂ and M are the same meaning as the preferred embodiment The same is true.

The monovalent substituent represented by R ₃ in the formula (2-2) includes a substituent group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. The group, substituted or unsubstituted heterocyclic group, more preferably an alkyl group or an aryl group substituted with an ionic hydrophilic group, particularly preferably an alkyl group substituted with an ionic hydrophilic group.

In the alkyl group substituted with the above ionic hydrophilic group, the alkyl group is preferably a methyl group, an ethyl group or a n-propyl group, and particularly preferably an ethyl group. As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -CO ₂ M ₁ , particularly preferably -CO ₂ Li.

The compound represented by the above formula (B-1) and formula (2-2) is preferably a compound represented by the following formula (3-2).

Hereinafter, the compound represented by the formula (3-2) or a salt thereof will be described in detail.

(In the formula (3-2), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , and X ₅ each independently represent a hydrogen atom or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counterbalance. cation)

Formula (3-2) in the G, R _2, R ₃ and M in the example are each independently the general formula G (2-2) in, R _2, R ₃ and examples of the same meaning as M, more The best case is the same.

In the formula (3-2), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ and X ₅ represent a substituent include the above-mentioned substituent group J.

X ₁ , X ₂ , X ₃ , X ₄ , and X _{5 are} preferably independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, substituted or Unsubstituted arylsulfonyl, nitro, substituted or unsubstituted alkoxycarbonyl, substituted or unsubstituted amide, substituted or unsubstituted sulfonamide, Preferably, it is a hydrogen atom, an ionic hydrophilic group, a cyano group, a methanesulfonyl group, a phenylsulfonyl group, a nitro group, a methoxycarbonyl group, an amine carbenyl group, particularly preferably a hydrogen atom or an ionic hydrophilic group ( It is preferably -SO ₃ M ₁ or -CO ₂ M ₁ , more preferably -CO ₂ M ₁ , particularly preferably -CO ₂ Li), or a cyano group.

In the formula (3-2), X ₂ and X ₄ are each preferably independently a hydrogen atom or an ionic hydrophilic group. X ₁ , X ₃ , and X _{5 are} preferably each independently a hydrogen atom or a substituent group J, and more preferably at least one of X ₁ , X ₃ , and X ₅ represents a σp value of Hammett. It is a pull electron base of 0.3 or more. The upper limit of the substituent constant σp value of Hammett is 1.0 or less.

If at least one of X ₁ , X ₃ , and X ₅ is a zeta electron group having a σp value in the range, the color of the azo compound can be adjusted, and the light fastness and the ozone gas firmness can be improved, and it can be used as an inkjet recording black. The ink can obtain an effect from the viewpoint of a water-soluble dye.

Specific examples of the electron withdrawing group having a σp value of 0.3 or more include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphine oxime. , diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfonylthio Aminesulfonyl, thiocyanate, thiocarbonyl, alkyl halide, halogenated alkoxy, halogenated aryloxy, halogenated alkylamino, halogenated alkylthio, other electrons with a σp value of 0.3 or more A substituted aryl, nitro, heterocyclic, halogen atom, azo group, or selenocyanate group. Preferred is a cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, an amine carbenyl group, a nitro group, more preferably a cyano group, a methylsulfonyl group or a nitro group.

In view of the color, the coloring power, and the water-soluble storage stability, at least one of X ₂ and X ₄ is preferably an ionic hydrophilic group, and preferably X ₁ , X ₃ , And X ₅ is a hydrogen atom or a Hammett having a σp value of 0.3 or more, more preferably X ₁ , X ₃ and X ₅ are hydrogen atoms, and X ₂ and X ₄ are ionic hydrophilic groups. As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -CO ₂ M ₁ , particularly preferably -CO ₂ Li.

The combination which is particularly preferable as the compound represented by the formula (3-2) is the following (i) to (iv).

(i) preferably at least one of X ₂ and X ₄ is an ionic hydrophilic group, and preferably X ₁ , X ₃ , and X ₅ are hydrogen atoms or the Hammert σp value is 0.3 or more. More preferably, X ₁ , X ₃ and X ₅ are a hydrogen atom, and X ₂ and X ₄ are ionic hydrophilic groups.

(ii) The monovalent substituent represented by R ₃ may, for example, be a substituted group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a heterocyclic group. More preferably, it is an alkyl group or an aryl group substituted with an ionic hydrophilic group.

(iii) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, and -CO ₂ M ₁ is more preferred, and -CO ₂ Li is particularly preferred.

(iv) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

As a preferable factor of the structure, the water solubility of the azo compound of the formula (3-2) and the association of the azo dye in the ink composition are remarkably improved, especially in the ink composition. Increased stability.

As a result, it can be stably stored for a long period of time, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, which is a preferred example.

The compound represented by the above formula (B-1), formula (2-2) or formula (3-2) is preferably a compound represented by the following formula (4-2).

Hereinafter, the compound represented by the formula (4-2) or a salt thereof will be described in detail.

(In the formula (4-2), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Independently representing a hydrogen atom or a monovalent counter cation)

Examples of R ₃ and M in the formula (4-2) are the same as the examples of R ₃ and M in the above formula (2-2), and the preferred examples are also the same.

In the general formula _{(4-2), X 1, X} 2, X 3, X 4, and X ₅ in the general formula (3-2) in the _{X 1, X 2, X 3} , X 4, and X ₅ The examples are the same and the preferred examples are the same.

The combination which is particularly preferable as the compound represented by the general formula (4) is the following (i) to (iv).

(i) A in the formula (B-1) is an aryl group having a substituent, and more preferably an aryl group having an ionic hydrophilic group or a Hammert having a σp value of 0.3 or more, and further A phenyl group having two ionic hydrophilic groups is preferred.

(ii) The monovalent substituent represented by R ₃ may, for example, be a substituted group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a heterocyclic group. More preferably, it is an alkyl group or an aryl group substituted with an ionic hydrophilic group, and particularly preferably an alkyl group substituted with an ionic hydrophilic group (preferably a methyl group, an ethyl group, or a n-propyl group, particularly preferably a positive C-propyl group). base).

(iii) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, and -CO ₂ M ₁ is more preferred, and -CO ₂ Li is particularly preferred.

(iv) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic A cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium). The salt to be formed is preferably a lithium salt, a sodium salt, a potassium salt or an ammonium salt, more preferably a lithium salt or a mixed salt containing a lithium salt as a main component, and most preferably a lithium salt.

The main reason for the structure is as follows: by the formula (B-1) The ring having G is not a nitrogen-containing 5-membered heterocyclic ring and becomes a thiophene ring, and the image retaining property of the printed matter using the ink composition of the present invention can be improved at a higher level (for example, ozone gas firmness, Light fastness), discoloration (color change), fading (decoloration), as a gray ink that requires little change in color and fading, the adaptability of black ink is improved.

The compound represented by the above formula (B-1), formula (2-2), formula (3-2) or formula (4-2) is preferably represented by the following formula (5-2). The compound represented.

(M ₂ independently represents a hydrogen atom or a monovalent counter cation, and when M ₂ represents a monovalent counter cation, it means a lithium ion, a sodium ion, a potassium ion, or an ammonium ion)

Examples of M ₂ in the formula (5-2) are each independently the same as the examples of M in the above formula (2-2), and preferred examples are also the same.

In addition, the azo compound represented by the general formula (B-1) is used as an aqueous solution of a dye (colorant) and a water-soluble ink composition, and a composition containing a color material such as a dye or a pigment and a dispersing agent (solvent or the like) is used. It can be used particularly suitably for image formation.

The compound represented by the above formula (B-1) is preferably a compound represented by the following formula (1-3).

Hereinafter, the compound represented by the formula (1-3) or a salt thereof will be described in detail.

(In the formula (1-3), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom, Or a monovalent substituent. Y ₂ , Y ₃ , and Y ₄ may be bonded to each other to form a ring. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent Counter cation)

Examples of G, R ₂ , Y ₂ , Y ₃ , Y ₄ and M in the formula (1-3) are each independently a G, R ₂ , Y ₂ , Y _{3 in the} above formula (B-1). Examples of Y ₄ and M have the same meaning, and preferred examples are also the same.

In the formula (1-3), X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent in the case where X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ represent a substituent include the above substituent J.

X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X _{7 are} preferably independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonate. A substituted or unsubstituted arylsulfonyl group, a nitro group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted amine carbenyl group, a substituted or unsubstituted amine Sulfhydryl group, more preferably hydrogen atom, ionic hydrophilic group, cyano group, methanesulfonyl group, phenylsulfonyl group, nitro group, methoxycarbonyl group, amine carbenyl group, particularly preferably hydrogen atom, ion Hydrophilic group, or cyano group.

In the formula (1-3), X ₁ , X ₃ , X ₅ and X ₇ are each independently a hydrogen atom or a substituent group J, and further preferably X ₂ and X ₄ . And at least one of X ₆ represents a tensile electron group having a σp value of 0.3 or more.

If at least one of X ₂ , X ₄ , and X ₆ is a zirconium group having a σp value in the range, the color of the azo compound can be adjusted, and the light fastness and the ozone gas firmness can be improved, and it can be used as an inkjet recording black. The ink can obtain an effect from the viewpoint of a water-soluble dye.

X ₂ , X ₄ , and X _{6 are} preferably independently a hydrogen atom, an ionic hydrophilic group, a cyano group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted aryl group. a sulfonyl group, a nitro group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted amine carbenyl group, a substituted or unsubstituted amine sulfonyl group, more preferably a hydrogen atom, an ion The hydrophilic group, the cyano group, the methanesulfonyl group, the phenylsulfonyl group, the nitro group, the methoxycarbonyl group, the amine carbenyl group, particularly preferably a hydrogen atom, an ionic hydrophilic group, or a cyano group.

Further, it is preferable that at least one of X ₂ , X ₄ and X ₆ represents a zestidine having a σp value of 0.3 or more, and an upper limit of the substituent constant σp of Hammett is 1.0 or less, more preferably X ₂ and X ₆ are ionic hydroxyl groups, and X ₄ represents a zestidine having a σp value of 0.3 or more.

Specific examples of the electron withdrawing group having a σp value of 0.3 or more include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphine oxime. , diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfonylthio Aminesulfonyl, thiocyanate, thiocarbonyl, alkyl halide, halogenated alkoxy, halogenated aryloxy, halogenated alkylamino, halogenated alkylthio, other electrons with a σp value of 0.3 or more A substituted aryl, nitro, heterocyclic, halogen atom, azo group, or selenocyanate group. Preferred is a cyano group, a methylsulfonyl group, a phenylsulfonyl group, a methoxycarbonyl group, an amine carbenyl group, a nitro group, more preferably a cyano group, a methylsulfonyl group or a nitro group.

In view of the color, the coloring power, and the water-soluble storage stability, at least one of X ₂ , X ₄ , and X ₆ is preferably an ionic hydrophilic group, and preferably X ₂ , At least one of X ₄ and X ₆ is an electron withdrawing group having a σp value of 0.3 or more of Hammett, and more preferably X ₃ is an electron withdrawing group having a σp value of 0.3 or more of Hammett, X ₂ , and X _{6 .} It is an ionic hydrophilic group. As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -SO ₃ M ₁ , particularly preferably -SO ₃ Li.

The combination which is particularly preferable as the compound represented by the general formula (1-3) is the following (i) to (v).

(i) G represents a nitrogen atom or -C(R ₂ )=, preferably -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine mercapto group, or a cyano group, preferably an aminomethyl group (-CONH ₂ group) or a cyano group, more preferably a cyano group.

(ii) Y ₂ , Y ₃ , and Y _{4 are} preferably independently a hydrogen atom, a substituted or unsubstituted heterocyclic amine group, an ionic hydrophilic group, a substituted or unsubstituted amine formazan. A substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted Any one of a mercaptoamine group, more preferably a hydrogen atom, a heterocyclic amine group having a substituted or unsubstituted amine group as a substituent, an ionic hydrophilic group, a substituted or unsubstituted alkyl group Any of a sulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted mercaptoamine group, particularly preferably a hydrogen atom, having a substituted or unsubstituted The amine group is a heterocyclic amine group as a substituent, an arylsulfonylamino group having an ionic hydrophilic group as a substituent, and a mercaptoamine group having an ionic hydrophilic group as a substituent. The mercaptoamine group is preferably an alkylcarbonylamino group, an alkylcarbonylamino group having an ionic hydrophilic group as a substituent, and an arylcarbonylamino group having an ionic hydrophilic group as a substituent. The alkyl group in the alkylcarbonylamino group is preferably a methyl group, an ethyl group or a n-propyl group, more preferably an ethyl group. As the aryl group in the arylcarbonylamino group, a phenyl group is preferred.

Most preferably, Y ₂ and Y ₄ represent a hydrogen atom, and Y ₃ is a heterocyclic amine group having a substituted or unsubstituted amino group as a substituent, and an arylsulfonyl group having an ionic hydrophilic group as a substituent. An amine group or a mercaptoamine group having an ionic hydrophilic group as a substituent.

(iii) as the ionic hydrophilic group, preferably -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -SO ₃ M ₁ , particularly preferably -SO ₃ Li.

(iv) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

(v) X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ are each independently a hydrogen atom or a substituent group J, more preferably a hydrogen atom or an ionic group. Hydrophilic group, cyano group, methanesulfonyl group, phenylsulfonyl group, nitro group, methoxycarbonyl group, amine carbenyl group, particularly preferably a hydrogen atom, an ionic hydrophilic group, or a cyano group. Preferably, X ₁ , X ₃ , X ₅ and X ₇ are each independently a hydrogen atom or a substituent group J, and further preferably at least one of X ₂ , X ₄ and X ₆ represents Hami. The specific σp value is an electron withdrawing group of 0.3 or more, and more preferably X ₄ is a zestidine having a σp value of 0.3 or more, and X ₂ and X ₆ are ionic hydrophilic groups. As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M ₁ (M ₁ represents a hydrogen atom or a monovalent counter cation), more preferably -SO ₃ M ₁ , particularly preferably -SO ₃ Li.

As a preferred reason for the structure, the water solubility of the azo compound of the formula (1-3) can be increased, and it can be electronically. An azo dye structure capable of coexisting with good color, coloring power, and high storage stability is provided three-dimensionally.

As a result, the storage stability of the ink composition is improved, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, and thus A preferred example.

The compound represented by the above formula (1-3) is preferably a compound represented by the following formula (2-3).

Hereinafter, the compound represented by the formula (2-3) or a salt thereof will be described in detail.

(In the formula (2-3), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently represented. a hydrogen atom, or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of G, R ₂ , X ₁ to X ₇ , and M in the formula (2-3) are independently and G, R ₂ , X ₁ to X ₇ in the above formula (1-3), and The examples of M have the same meaning, and the preferred examples are also the same.

The monovalent substituent represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ in the formula (2-3) may, for example, be a substituent group A', preferably a substituted or unsubstituted alkane. The aryl group, the substituted or unsubstituted aryl group, the substituted or unsubstituted heterocyclic group, more preferably an alkyl group substituted with an ionic hydrophilic group or an aryl group substituted with an ionic hydrophilic group.

Among R ₁₁ and R ₁₂ , one is preferably a hydrogen atom, and the other is a hydrogen atom or an alkyl group or an aryl group having an ionic hydrophilic group. Among R ₁₃ and R ₁₄ , one is preferably a hydrogen atom, and the other is a hydrogen atom or an alkyl group or an aryl group having an ionic hydrophilic group.

In particular, one of the substituents (R ₁₁ and R ₁₂ ) which becomes an amine group on the s-triazine ring is a hydrogen atom, and the other is an alkyl group having an ionic hydrophilic group or an aryl group, (R _{One of 13} and R ₁₄ ) is a hydrogen atom, and the other is an alkyl group having an ionic hydrophilic group or a combination of aryl groups, and the water solubility of the dye and the association of the dye in water solubility are improved (dye molecule) In view of this, it is preferable to improve the storage stability of the water-soluble ink required for the water-soluble ink for inkjet (preventing the precipitation of the dye and suppressing the decomposition of the dye).

The compound represented by the above formula (B-1) and formula (2-3) is preferably a compound It is a compound represented by the following general formula (3-3).

Hereinafter, the compound represented by the formula (3-3) or a salt thereof will be described in detail.

(In the formula (3-3), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ And X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of X ₁ to X ₇ , R ₁₁ to R ₁₄ , and M in the formula (3-3) are independently and independently from X ₁ to X ₇ and R ₁₁ to R ₁₄ in the above formula (2-3). The examples of M and M have the same meaning, and the preferred examples are also the same.

The compound represented by the above formula (B-1) and formula (2-3) is preferably a compound represented by the following formula (4-3).

Hereinafter, the compound represented by the formula (4-3) or a salt thereof will be described in detail.

(In the formula (4-3), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ And X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of X ₁ to X ₇ , R ₁₁ to R ₁₄ , and M in the formula (4-3) are independently and independently from X ₁ to X ₇ and R ₁₁ to R ₁₄ in the above formula (2-3). The examples of M and M have the same meaning, and the preferred examples are also the same.

The combination which is particularly preferable as the compound represented by the general formula (2-3), the general formula (3-3), and the general formula (4-3) is the following (i) to (iv).

(i) The monovalent substituent represented by R ₁₁ to R ₁₄ may, for example, be a substituted group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, The substituted or unsubstituted heterocyclic group is more preferably an alkyl group substituted with an ionic hydrophilic group or an aryl group substituted with an ionic hydrophilic group.

(ii) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, -SO ₃ M ₁ is more preferred, and -SO ₃ Li is particularly preferred.

(iii) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

(iv) preferably at least one of X ₂ , X ₄ , and X ₆ is an ionic hydrophilic group, and preferably at least one of X ₂ , X ₄ , and X ₆ has a σp value of 0.3 of Hammett. More preferably, X ₄ is a zestidine having a σp value of 0.3 or more, and X ₂ and X ₆ are ionic hydrophilic groups.

Preferred examples of the structure include water solubility of the azo compound of the formula (2-3), formula (3-3), and formula (4-3) and azo in the ink composition. The association of the pigment is remarkably improved, especially the high storage stability in the ink composition.

As a result, it can be stably stored for a long period of time, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, which is a preferred example.

The compound represented by the above formula (1-3) is preferably a compound represented by the following formula (2-4).

Hereinafter, the compound represented by the formula (2-4) or a salt thereof will be described in detail.

(In the formula (2-4), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. R ₃ represents a monovalent substituent. M independently represents a hydrogen atom. Or a monovalent counter cation)

Examples of G, X ₁ to X ₇ , R ₂ and M in the formula (2-4) are independently the same as G, X ₁ to X ₇ , R ₂ and M in the above formula (1-3). The examples have the same meaning, and the preferred examples are also the same.

The monovalent substituent represented by R ₃ in the formula (2-4) may, for example, be a substituent group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group. The group or the heterocyclic group is more preferably an alkyl group or an aryl group substituted with an ionic hydrophilic group.

The compound represented by the above formula (1-3) and formula (2-4) is preferably a compound represented by the following formula (3-4).

Hereinafter, the compound represented by the formula (3-4) or a salt thereof will be described in detail.

(In the formula (3-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent Substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of M, R ₃ and X ₁ to X ₇ in the formula (3-4) are independently and in the above formula (2-4), examples of M, R ₃ and X ₁ to X ₇ are The same meaning and preferred examples are the same.

The combination which is particularly preferable as the compound represented by the general formula (2-4) and the general formula (3-4) is the following (i) to (iv).

(i) The monovalent substituent represented by R ₃ may, for example, be a substituent group A', preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a heterocyclic group. More preferably, it is an alkyl group or an aryl group substituted with an ionic hydrophilic group.

(ii) As the ionic hydrophilic group, -SO ₃ M ₁ or -CO ₂ M _{1 is} preferred, -SO ₃ M ₁ is more preferred, and -SO ₃ Li is particularly preferred.

(iii) The above M ₁ and M each independently represent a hydrogen atom or a monovalent counter cation, and examples of the monovalent counter cation include an ammonium ion, an alkali metal ion (for example, lithium ion, sodium ion, potassium ion) and organic a cation (for example, tetramethylammonium ion, tetramethylphosphonium ion, tetramethylphosphonium), preferably a lithium salt, a sodium salt, a potassium salt, an ammonium salt, more preferably a lithium salt or a lithium salt as a main component The salt is mixed, preferably a lithium salt.

(iv) preferably at least one of X ₂ , X ₄ , and X ₆ is an ionic hydrophilic group, and preferably at least one of X ₂ , X ₄ , and X ₆ has a σp value of 0.3 of Hammett. More preferably, X ₄ is a zestidine having a σp value of 0.3 or more, and X ₂ and X ₆ are ionic hydrophilic groups.

The reason why the azo compound of the general formulae (2-4) and (3-4) has a water solubility and the association of the azo dye in the ink composition is remarkably improved. In particular, the high storage stability in the ink composition is improved.

As a result, it can be stably stored for a long period of time, and the light fastness, thermal stability, moist heat stability, water resistance, gas resistance, and/or solvent resistance which are required properties of the ink are greatly improved, which is a preferred example.

The compound represented by the above formula (1-3) or formula (2-4) is preferably a compound represented by the following formula (4-4).

Hereinafter, the compound represented by the formula (4-4) or a salt thereof will be described in detail.

(In the formula (4-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent Substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of the general formula (4-4) in R _3, and X ₁ ~ X ₇ and M are each independently of examples of the general formula R (2-4) _3, and X ₁ ~ X ₇ and M is The same meaning and preferred examples are the same.

The azo compound represented by the above formula (B-1) is preferably an azo compound represented by the following formula (6).

General formula (6)

(In the formula (6), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ are each independently represented. a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and M in the formula (6) are each independently and X ₁ , X ₂ , X ₃ and X ₄ in the above formula (3-1). Examples of X ₅ and M have the same meaning, and preferred examples are also the same.

Formula (6) Y _2, Y _3, and Y ₄ are each independently examples with the general formula Y (B-1) is _2, Y _3, and Y ₄ are examples of the same meaning as the preferred embodiment The same is true.

The azo compound represented by the above formula (B-1) is preferably an azo compound represented by the following formula (7).

General formula (7)

(In the formula (7), X ₁ , X ₂ , X ₃ , X ₄ and X ₅ each independently represent a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ are each independently represented. a hydrogen atom or a monovalent substituent. Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of Y ₂ , Y ₃ , Y ₄ , X ₁ to X ₅ and M in the formula (7) are independently and Y ₂ , Y ₃ , Y ₄ , X ₁ to X in the above formula (6), respectively. The examples of ₅ and M have the same meaning, and the preferred examples are also the same.

The azo compound represented by the above formula (B-1) and formula (7) is preferably an azo compound represented by the following formula (8).

Formula (8)

In addition, the ink composition containing the azo compound represented by the general formula (2-3) as a coloring matter (colorant) means a composition containing a color material such as a dye or a pigment and a dispersing agent (solvent or the like), which is particularly suitable. Used for image formation.

(In the formula (2-3), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently represented. a hydrogen atom, or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of G, R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ to X ₇ and M in the formula (2-3) are independently and G in the above formula (2-3) Examples of R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ to X ₇ and M have the same meanings, and preferred examples are also the same.

The azo compound represented by the above formula (2-3) is preferably an azo compound represented by the following formula (4-3).

(In the formula (4-3), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ And X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. M independently represents a hydrogen atom or a monovalent counter cation)

Examples of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , X ₁ to X ₇ and M in the formula (4-3) are each independently R ₁₁ and R ₁₂ in the above formula (4-3). Examples of R ₁₃ , R ₁₄ , X ₁ to X ₇ and M have the same meanings, and preferred examples are also the same.

Further, an azo compound represented by the general formula (2-4) is used as a pigment The ink composition of the (colorant) means a composition containing a color material such as a dye or a pigment and a dispersing agent (solvent or the like), and can be particularly suitably used for image formation.

(In the formula (2-4), G represents a nitrogen atom or -C(R ₂ )=. R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent substituent. R ₃ represents a monovalent substituent. M independently represents a hydrogen atom. Or a monovalent counter cation)

The azo compound represented by the above formula (2-4) is preferably an azo compound represented by the following formula (3-4).

General formula (3-4)

(In the formula (3-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent Substituent. M independently represents a hydrogen atom or a monovalent counter cation)

The azo compound represented by the above formula (2-4) is preferably an azo compound represented by the following formula (4-4).

(In the formula (4-4), R ₃ represents a monovalent substituent. X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and X ₇ each independently represent a hydrogen atom or a monovalent Substituent. M independently represents a hydrogen atom or a monovalent counter cation)

From the general formula (B-1), the general formula (2-1), the general formula (2-2), the general formula (2-3), the general formula (2-4), the general formula (3-1), Formula (3-2), Formula (3-3), Formula (3-4), Formula (4-1), Formula (4-2), Formula (4-3), Formula ( 4-4) The maximum absorption wavelength (λ _max ) of the absorption spectrum measured by the compound represented by the formula (5) to the formula (7) or the formula (8) using water as a solvent is preferably 550 nm or more and 700 nm or less. Further, it is particularly preferably 580 nm to 650 nm.

Further, in the present invention, the formula (B-1), the formula (2-1), the formula (2-2), the formula (2-3), the formula (2-4), and the formula (3-1), general formula (3-2), general formula (3-3), general formula (3-4), general formula (4-1), general formula (4-2), general formula (4) -3) The compound represented by the formula (4-4), the formula (5) to the formula (7), and the formula (8) preferably has at least three or more ionic hydrophilic groups. More preferably, it has 3 to 6 ionic hydrophilic groups, and more preferably has 4 to 5 ionic hydrophilic groups. Thereby, the water absorbing effect of the azo compound and the storage stability of the aqueous solution are improved, and the required performance as a water-soluble dye for inkjet recording black ink is satisfied at a high level, and further, when it is used as an ink for inkjet recording, The quality of the inkjet print.

From the general formula (B-1), the general formula (2-1), the general formula (2-2), the general formula (2-3), the general formula (2-4), the general formula (3-1), General formula (3-2), general formula (3-3), general formula (3-4), general formula (4-1), general formula (4-2), general formula (4-3), general formula In the azo compound represented by the formula (5) to the formula (7) or the formula (8), at least one M is preferably a lithium ion.

Further, in the present invention, even the general formula (B-1), the general formula (2-1), the general formula (2-2), the general formula (2-3), the general formula (2-4), and the Formula (3-1), Formula (3-2), Formula (3-3), Formula (3-4), Formula (4-1), Formula (4-2), Formula ( 4-3), The compound represented by the formula (4-4), the formula (5) to the formula (7), and the formula (8) may be used as an isotope (for example, 2H, 3H, 13C, or 15N).

The following formula (B-1), formula (2-1), formula (2-2), formula (2-3), formula (2-4), and formula (3-1) are shown. ), general formula (3-2), general formula (3-3), general formula (3-4), general formula (4-1), general formula (4-2), general formula (4-3), Specific examples of the compound represented by the formula (4-4) and the formula (5) to the formula (7), but the compound used in the present invention is not limited to the following examples. M represents a hydrogen atom or a monovalent counter cation (lithium ion, sodium ion, potassium ion, or ammonium ion).

The dye represented by the formula (B-1) may also be in a state in which a mixed salt of a plurality of M is present. When the dye represented by the formula (B-1) is a mixed salt, among the Ms of the dye represented by the formula (B-1) contained in the ink, the molar fraction is used. Preferably, 50% to 100%, more preferably 80% to 100%, of M is Li ⁺ ions, and particularly preferably 90% to 100% of M is Li ⁺ ions. M other than the Li ⁺ ion is preferably a Na ⁺ ion or an NH ₄ ⁺ ion, more preferably a Na ⁺ ion.

Further, the dye represented by the formula (B-1) is not a mixed salt, and all of the dyes represented by the formula (B-1) contained in the ink are preferably Li. The reason for this is that, by all of M being Li, in the state of molecular dispersion dissolved in an aqueous solution or an ink solution, the carboxyl group or the salt (-CO ₂ M) which is an ionic hydrophilic group is dissociated and ionized into -CO ₂ ^- When M ⁺ is exchanged in this state, it is possible to obtain a state in which a salt having a lower solubility in an aqueous solution or an ink solution is formed, and it is easy to suppress precipitation in a state of a salt of a colorant.

The dye represented by the formula (B-1) can be synthesized by a general synthesis method, for example, by a coupling reaction of a diazo component and a coupler. Specifically, it can be synthesized by the method described in JP-A-2003-306623 or JP-A-2005-139427.

Further, in the present invention, in order to adjust the color tone of the black ink composition, etc., the light resistance may not be greatly impaired. In the range of ozone resistance, a compound represented by the following formula (B-11) is used in combination, and other yellow dyes are used in combination.

Examples of the yellow-based dye to be used together include CI 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, CI Acid Yellow 17, 19, 23, 25, 39, 40, 42 , 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, and 40, etc., but not limited to these dye.

General formula (B-11): G ₁ -N=NG ₂ -LK

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

Examples of the aryl group include a benzene ring or a naphthalene ring, and examples of the hetero atom of the hetero ring include N, O, and S. An aliphatic ring, an aromatic ring or other heterocyclic ring may be condensed in the heterocyclic ring. As the substituent, it may be an arylazo group or a heterocyclic azo group.

The compound represented by the formula (B-11) is preferably a compound represented by the following formula (B-12).

General formula (B-12): G ₁ -N=NG ₂ -L ₁ -G ₃ -N=NG ₄

In the formula (B-12), G ₁ , G ₂ , G ₃ and G ₄ each independently represent an aryl group which may be substituted or a heterocyclic group which may be substituted. L ₁ represents a divalent linking group. Among them, the general formula (B-12) has at least one ionic hydrophilic group.

The compound represented by the formula (B-12) is preferably a compound represented by the following formula (B-13).

General formula (B-13): E ₁ -N=NE ₂ -N=NL ₁₁ -N=NE ₃ -N=NE ₄

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

The compound represented by the formula (B-13) is preferably a compound represented by the following formula (B-14).

In the formula (B-14), the A ring, the B ring, and the C ring each independently represent an aryl group which may be substituted or a heterocyclic group which may be substituted.

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 and C ₁₄ each independently represent a hydrogen atom or a substituent. Among them, the 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) will be described.

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 and 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 mercaptoamine group, a substituted or unsubstituted sulfonylamino group, Substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, substituted or unsubstituted alkane a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted amine carbenyl group, preferably an ionic hydrophilic group a radical, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted mercaptoamine group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, substituted or unsubstituted Substituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted sulfonyl, more preferably ionic hydrophilic, halogen, cyano, nitro Substituted or unsubstituted mercaptoamine, substituted or unsubstituted alkyl, especially preferably ion Hydrophilic group.

Q ₁ and Q ₂ are each independently, preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, more preferably It is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom.

L ₁₂ represents a divalent linking group, preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted phenylene group, a carbonyl group, a substituted or unsubstituted group. 1,3,5-triazine-2,4-diyl, more preferably carbonyl, substituted or unsubstituted 1,3,5-triazine-2,4-diyl, particularly preferably carbonyl.

Specific examples of the compound represented by the above formula (B-11), formula (B-12), formula (B-13), and formula (B-14) are shown below, but are used in the present invention. The compound is not limited to the following examples.

The content of the compound represented by the above formula (B-1) or a salt thereof in the black ink composition is preferably from 0.1% by mass to 20% by mass, more preferably 0.5% by mass based on the total mass of the black ink composition. %~15% by mass, and more preferably 1% by mass to 10% by mass.

In addition, the black ink composition is relative to the total mass of the black ink composition. The total amount of all the colorants contained is preferably from 0.1% by mass to 30% by mass, more preferably from 0.5% by mass to 20% by mass, even more preferably from 1% by mass to 15% by mass.

When the total amount of the coloring agent contained in the black ink composition is 0.1% by mass or more, when an image or the like is recorded on a recording medium using the ink composition, a sufficiently good color development or high image can be obtained. Like concentration. In addition, by setting the total amount of the coloring agent to 30% by mass or less, the viscosity of the ink composition can be adjusted to a preferable value, and the discharge amount of the ink composition from the inkjet head can be stabilized. Further, clogging of the ink jet head can be prevented.

Light resistance of a dye as a compound represented by the above formula (B-1) or a salt thereof. Ozone resistance is very excellent, so by making the ink set combined with the yellow ink, cyan ink and magenta ink of the present invention, the light resistance of each color can be made. Ozone resistance is dramatically improved, even in light. After the ozone exposure test, the color balance of the image will not collapse, and the image quality can be maintained for a long time.

Further, in the black ink composition, a dye which is a compound represented by the above formula (B-1) or a salt thereof and a compound which can be used in the above-mentioned invention can be used in combination to adjust to a better color. Balanced and maintains the print quality of the prints in a longer period of time.

(cyan ink)

The coloring agent used in the cyan ink composition constituting the ink set of the present invention will be described.

In the cyan ink composition of the present invention, a phthalocyanine dye represented by the following formula (1) used as a cyan dye, and a phthalocyanine represented by the following formula (2) are contained. The dye acts as a colorant.

[Phthalocyanine dye represented by the general formula (1)]

First, the phthalocyanine dye represented by the general formula (1) will be described in detail.

In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime A group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group. These groups may further have a substituent.

Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or Unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, 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 and q ₄ each independently represent 1 or 2.

M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime A group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group. These groups may further have a substituent. The substituent described in the above substituent group A is mentioned as a substituent.

Examples of the halogen atom represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ include a fluorine atom, a chlorine atom and a bromine atom.

The alkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 when the substituent is removed. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom and an ionic hydrophilic group. Examples of the alkyl group include methyl group, ethyl group, butyl group, isopropyl group, tert-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, 3-sulfopropyl group and 4 - sulfobutyl.

The cycloalkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

The aralkyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenylethyl group.

The aryl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when the substituent is removed is preferred. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamine group, and an ionic hydrophilic group. Examples of the aryl group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and a m-(3-sulfopropylamino)phenyl group.

The heterocyclic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ 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 ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, and a 2-furyl group.

The alkylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylamino group having a substituent and an unsubstituted alkylamino group. The alkylamine group is preferably an alkylamine group having 1 to 6 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.

The alkoxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxy group having a substituent and an unsubstituted alkoxy group. The alkoxy group in the case of removing a substituent is preferably an alkoxy group having 1 to 12 carbon atoms. Examples of the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxy group having a substituent and an unsubstituted aryloxy group. The aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

The guanamine group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a decylamino group having a substituent and an unsubstituted guanamine group. The guanamine group is preferably a guanamine group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the guanamine group include an acetamino group, a propylamine group, a benzamidine group, and a 3,5-disulfobenzylammonium group.

The arylamine group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylamino group having a substituent and an unsubstituted arylamine group. The arylamine group is preferably an arylamine group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include a halogen atom and an ionic hydrophilic group. Examples of the arylamine group include an anilino group and a 2-chloroanilino group.

The ureido group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a ureido group having a substituent and an unsubstituted ureido group. As the ureido group, a ureido group having 1 to 12 carbon atoms when the substituent is removed is preferred. Examples of the substituent include an alkyl group and an aryl group. Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylureido group, and a 3-phenylureido group.

The amine sulfonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aminesulfonylamino group having a substituent, and an unsubstituted amine Sulfhydrylamino group. Examples of the substituent include an alkyl group. Examples of the aminesulfonylamino group include N,N-dipropylaminesulfonylamino.

The alkylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkylthio group having a substituent and an unsubstituted alkylthio group. The alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylthio group include a methylthio group and an ethylthio group.

The arylthio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an arylthio group having a substituent and an unsubstituted arylthio group. The arylthio group is preferably an arylthio group having 6 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an alkyl group and an ionic hydrophilic group. Examples of the arylthio group include a phenylthio group and a p-tolylthio group.

The alkoxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonylamino group having a substituent, and an unsubstituted alkane. Oxycarbonylamino group. The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

The sulfonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfonylamino group having a substituent and an unsubstituted sulfonamide group. The sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the sulfonamide group include methotrexate, benzenesulfonamide, and 3-carboxybenzenesulfonamide.

The amine mercapto group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an amine carbenyl group having a substituent, and an unsubstituted amine carbenyl group. Examples of the substituent include an alkyl group. Examples of the amine mercapto group include a methylamine methyl thiol group and a dimethylamine carbaryl group.

The amine sulfonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aminesulfonyl group having a substituent, and an unsubstituted sulfonamide group. Examples of the substituent include an alkyl group and an aryl group. Examples of the amine sulfonyl group include dimethylamine sulfonyl group and bis-(2-hydroxyethyl)amine sulfonyl group, phenylamine sulfonyl group.

The alkoxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The heterocyclic oxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a heterocyclic oxy group having a substituent and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group is preferably a heterocyclic oxy group having a 5-membered or 6-membered ring. Examples of the substituent include a hydroxyl group and an ionic hydrophilic group. Examples of the heterocyclic oxy group include 2-tetrahydropyranyloxy.

The azo group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an azo group having a substituent and an unsubstituted azo group. Examples of the azo group include a p-nitrophenylazo group.

The decyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a decyloxy group having a substituent and an unsubstituted decyloxy group. The decyloxy group is preferably a decyloxy group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the decyloxy group include an ethoxylated group and a benzamidineoxy group.

The amine methyl methoxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an amine methyl methoxy group having a substituent, and an unsubstituted amine formazan. Oxygen. Examples of the substituent include an alkyl group. Examples of the amine methyl methoxy group include N-methylamine methyl methoxy group.

The decyloxy group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a decyloxy group having a substituent and an unsubstituted decyloxy group. Examples of the substituent include an alkyl group. Examples of the decyloxy group include a trimethyldecyloxy group.

The aryloxycarbonyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

The aryloxycarbonylamino group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes an aryloxycarbonylamino group having a substituent, and an unsubstituted aromatic group. Oxycarbonylamino group. The aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group.

The quinone imine group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a fluorenylene group having a substituent and an unsubstituted quinone group. Examples of the quinone imine group include N-phthalimido group and N-succinimide group.

The heterocyclic thio group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. As the heterocyclic thio group, a heterocyclic ring having a 5-membered ring or a 6-membered ring is preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The phosphonium group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a phosphonium group having a substituent and an unsubstituted phosphonium group. Examples of the phosphonium group include a phenoxyphosphonium group and a phenylphosphonium group.

The fluorenyl group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a fluorenyl group having a substituent and an unsubstituted fluorenyl group. The fluorenyl group is preferably a fluorenyl group having 1 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of sulfhydryl groups include ethenyl and benzhydryl groups.

The ionic hydrophilic group represented by R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ includes a sulfo group, a carboxyl group, a quaternary ammonium group and the like. The ionic hydrophilic group is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group. The carboxyl group and the sulfo group may also be in the form of a salt, and examples of the counter ion forming a salt include an alkali metal ion (for example, sodium ion, potassium ion) and an organic cation (for example, tetramethylphosphonium ion).

Wherein R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 are} preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group or a decylamino group. The ureido group, the sulfoximine group, the amine carbaryl group, the amine sulfonyl group and the alkoxycarbonyl group are particularly preferably a hydrogen atom, a halogen atom or a cyano group, and most preferably a hydrogen atom.

In the formula (1), Z ₁ , Z ₂ , Z ₃ and Z ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted. Alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic. Among them, at least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. The substituent described in the above substituent group A is mentioned as a substituent.

The alkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ 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 when the substituent is removed. Examples of the substituent include: a hydroxyl group, an alkoxy group, a cyano group, an alkylamino group (RNH-, RR'N-), an amine mercapto group (-CONHR), an amine sulfonyl group (-SO ₂ NHR, -SO) ₂ NRR'), sulfonylamino group (-NHSO ₂ R), -SONHR group, -SONRR' group, halogen atom and ionic hydrophilic group. Further, R and R' represent an alkyl group or a phenyl group, and these may further have a substituent. Examples of the substituent include an alkylamine group, a hydroxyl group, an ionic hydrophilic group, and the like. R, R' Examples of the alkyl group which can be formed by chemical bonding include: methyl, ethyl, butyl, n-propyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyano Base, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.

The cycloalkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ 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 when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The alkenyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an alkenyl group having a substituent and an unsubstituted alkenyl group. The alkenyl group is preferably an alkenyl group having 2 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group, an allyl group and the like.

The aralkyl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms when the substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenylethyl group.

The aryl group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group, an aryl group having 6 to 12 carbon atoms when the substituent is removed is preferred. Examples of the aryl group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and a m-(3-sulfopropylamino)phenyl group, an m-sulfophenyl group. Examples of the substituent include an alkyl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N-), an amine mercapto group (-CONHR), an amine sulfonyl group (- SO ₂ NHR), sulfonylamino group (-NHSO ₂ R), halogen atom, ionic hydrophilic group (further, R, R' above represents an alkyl group, a phenyl group, and these may further have an ionic hydrophilic group Sex base).

The heterocyclic group represented by Z ₁ , Z ₂ , Z ₃ , and Z ₄ includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group, and may further form a condensed ring with another ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. The heterocyclic group may further form a condensed ring with other rings. In the examples of the heterocyclic group, if the substitution positions of the heterocyclic ring are not limited, they respectively include imidazole, benzimidazole, pyrazole, benzopyrazole, triazole, thiazole, benzothiazole, isothiazole, and Benzoisothiazole, oxazole, benzoxazole, thiadiazole, oxadiazole, pyrrole, benzopyrrole, indole, isoxazole, benzisoxazole, thiophene, benzothiophene, furan, benzo Furan, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, porphyrin, pyridazine, quinazoline, quinoxaline, triazine, and the like. Examples of the substituent include an alkyl group (R-), an aryl group (R-), an alkoxy group (RO-), an alkylamino group (RNH-, RR'N-), an amine formazan group (-CONHR). Aminesulfonyl (-SO ₂ NHR), sulfonylamino (-NHSO ₂ R), sulfonyl (-SO ₂ R), mercaptoamine (-NHCOR), halogen atom, ionic hydrophilicity Further, R and R' above represent an alkyl group or an aryl group, and these may further have an ionic hydrophilic group or a substituent having an ionic hydrophilic group.

Z ₁ , Z ₂ , Z ₃ , and Z _{4 are} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, more preferably a The substituted alkyl group, the substituted aryl group, the substituted heterocyclic group, and more preferably the substituted alkyl group.

At least one of Z ₁ , Z ₂ , Z ₃ , and Z ₄ has an ionic hydrophilic group as a substituent. The ionic hydrophilic group as a substituent includes a sulfo group, a carboxyl group, a quaternary ammonium group, and the like. The ionic hydrophilic group is preferably a carboxyl group or a sulfo group, and particularly preferably a sulfo group. The carboxyl group and the sulfo group may also be in the form of a salt, and examples of the counter ion forming a salt include an alkali metal ion (for example, sodium ion, potassium ion) and an organic cation (for example, tetramethylphosphonium ion).

In the formula (1), l, m, n and p each independently represent the ground 1 or 2. That is, 4≦l+m+n+p≦8 is satisfied. It is preferable to satisfy 4≦l+m+n+p≦6, and it is preferable that l, m, n, and p are 1 (l=m=n=p=1), respectively.

In the formula (1), q ₁ , q ₂ , q ₃ and q ₄ each independently represent 1 or 2. Particularly preferably q ₁ = q ₂ = q ₃ = q ₄ = 2.

In the formula (1), M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide.

As M ₁ other than a hydrogen atom are preferred, as the metal element include: Li, Na, K, Mg , Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and the like. Among them, Cu, Ni, Zn, Al, etc. are particularly preferable, and Cu is most preferable. As the metal oxide, VO, GeO, or the like is preferably exemplified. Further, as the metal hydroxide, Si(OH) ₂ , Cr(OH) ₂ , Sn(OH) ₂ or the like is preferably exemplified. Further, examples of the metal halide include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl.

[Phthalocyanine dye represented by the general formula (2)]

Next, the phthalocyanine dye represented by the general formula (2) will be described in detail.

In the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently and have the meanings respectively R ₂ and R ₃ in the above formula (1). R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 are the} same.

Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently and have the same meanings as Z ₁ , Z ₂ , Z ₃ , and Z ₄ in the above formula (1), respectively.

t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.

The same meaning as M in the general formula M ₂ (1) _1.

R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently and have the meanings respectively R ₂ , R ₃ , R ₆ , R ₇ in the above formula (1), R ₁₀ , R ₁₁ , R ₁₄ and R _{15 are the} same, preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, a decylamino group, a ureido group, a sulfonylamino group, an amine formazan group. The group, the amine sulfonyl group and the alkoxycarbonyl group are particularly preferably a hydrogen atom, a halogen atom or a cyano group, and most preferably a hydrogen atom.

These groups may further have a substituent. The substituent described in the above substituent group A is mentioned as a substituent.

Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently and have the same meanings as Z ₁ , Z ₂ , Z ₃ , and Z ₄ in the above formula (1), respectively.

Z ₅ , Z ₆ , Z ₇ , and Z _{8 are} preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, more preferably a The substituted alkyl group, the substituted aryl group, the substituted heterocyclic group, and more preferably the substituted alkyl group. Further, from the viewpoint of ozone solidity, at least one of the substituents which the most preferred substituted alkyl group has is a -SONHR group (wherein R represents a substituted or unsubstituted alkyl group, or substituted or Unsubstituted phenyl).

The meaning of the ionic hydrophilic group as a substituent possessed by at least one of Z ₅ , Z ₆ , Z ₇ , and Z ₈ is Z ₁ , Z ₂ , Z ₃ , and Z in the above formula (1) The ionic hydrophilic groups having _four substituents are the same, and preferred examples are also the same.

In the formula (2), t, u, v and w each independently represent 1 or 2. That is, 4≦t+u+v+w≦8 is satisfied. Preferably, 4 ≦ t + u + v + w ≦ 6 is satisfied, and it is preferable that t, u, v, and w are 1 (t = u = v = w = 1), respectively.

In the formula (2), q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2. Particularly preferably q ₅ = q ₆ = q ₇ = q ₈ = 2.

Meaning M ₂ M ₁ in the general formula the same (1), preferred embodiments are also the same.

[Synthesis of phthalocyanine dye]

For example, it can be issued by Shirai-Kobayashi and IPC (shares). And function-"(P.1~P.62), CC Reitz Love and ABP Lewell (CCLeznoff-ABPLever), VCH issued "Phthalocyanines-Properties and Applications" The phthalocyanine derivative used in the present invention is synthesized by a method described in (P.1 to P.54) or the like or a method similar to the methods.

Hereinafter, the synthesis of the phthalocyanine dye represented by the general formula (2) will be described as an example.

In the phthalocyanine dye represented by the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are hydrogen, q ₅ , q ₆ , q ₇ and The compound wherein q ₈ is 2 is, for example, a phthalonitrile derivative represented by the following formula (V), and/or a diimine group represented by the following formula (VI) The isoindoline derivative is synthesized by reacting with a metal derivative represented by the following M-(Y)d.

In the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are each independently and have the meanings respectively R ₂ and R ₃ in the above formula (1). R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R _{15 are the} same. Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently and have the same meanings as Z ₁ , Z ₂ , Z ₃ , and Z ₄ in the above formula (1), respectively.

t, u, v, w, q ₅ , q ₆ , q ₇ and q ₈ each independently represent 1 or 2.

M and M _{2 have} the same meanings as M ₁ in the above formula (1), and M = M ₂ .

In the general formula (V) and/or the general formula (VI), x has the same meaning as t, u, v, and w in the general formula (2). Z represents a substituent corresponding to Z ₅ , Z ₆ , Z ₇ , and Z ₈ .

Y represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, acetamidine acetone or oxygen, and d is an integer of 1 to 4.

Examples of the metal derivative represented by M-(Y)d include Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Ru, Rh, Pd, In, and Sn. Pt, a halide of Pb, a carboxylic acid derivative, a sulfate, a nitrate, a carbonyl compound, an oxide, a complex, and the like. Specific examples include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, and bromine. Zinc, zinc iodide, zinc acetate, vanadium chloride, vanadium oxychloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, manganese acetylacetonate, manganese chloride, chlorination Lead, lead acetate, indium chloride, titanium chloride, tin chloride, and the like.

The metal derivative and the phthalonitrile compound represented by the general formula (V) are preferably used in a molar ratio of 1:3 to 1:6. Further, the amount of the metal derivative and the diimidoisoindoline derivative represented by the general formula (VI) is preferably from 1:3 to 1:6 in terms of a molar ratio.

The reaction is usually carried out in the presence of a solvent. As the solvent, an organic solvent having a boiling point of 80 ° C or higher, preferably 130 ° C or higher can be used. For example, n-pentanol, n-hexanol, Cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol, propylene glycol, ethoxyethanol, Propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, trichlorobenzene, chloronaphthalene, cyclobutyl hydrazine, nitrobenzene, quinoline, urea, and the like. The solvent is used in an amount of from 1 to 100 times by mass, preferably from 5 to 20 times by mass, based on the mass of the phthalonitrile compound.

In the reaction, 1,8-diazabicyclo[5.4.0]-7-undecene (1,8-Diazabicyclo[5.4.0]-7-undecene, DBU) or ammonium molybdate may also be added as a touch. Media. The amount of addition is 0.1 times moles to 10 times moles, preferably 0.5 times moles to 2 times moles, relative to the phthalonitrile compound and/or the diimidoisoindoline derivative 1 mole.

It is preferably carried out in the range of a reaction temperature of from 80 ° C to 300 ° C, preferably from 100 ° C to 250 ° C, and particularly preferably in the range of from 130 ° C to 230 ° C. If it is less than 80 ° C, the reaction rate is extremely slow. If it exceeds 300 ° C, decomposition of the phthalocyanine compound may occur.

It is preferably carried out in a reaction time of from 2 hours to 20 hours, preferably from 5 hours to 15 hours, and particularly preferably in the range of from 5 hours to 10 hours. If it is less than 2 hours, many unreacted raw materials exist, and if it exceeds 20 hours, decomposition of a phthalocyanine compound may generate.

The product obtained by these reactions can be used as a product after being treated according to a post-treatment method of a usual organic synthesis reaction, followed by purification or not. That is, for example, it may be provided as a product without refining the liberation from the reaction system, or may be subjected to recrystallization or column chromatography (for example, gel permeation chromatography (SEPHADEXTM LH-20: Pharmacia ( Pharmacia) The refining operation is carried out separately or in combination and is provided as a product. Further, after the completion of the reaction, the reaction solvent may be distilled off, or may be added to water or ice for neutralization without being distilled off, or may be provided as a product without being neutralized, and may be purified as a product; or The operation of refining by recrystallization, column chromatography, or the like is carried out separately or in combination, and then provided as a product. In addition, after the completion of the reaction, the reaction solvent may be distilled off, or may be added to water or ice for neutralization without being distilled off, or may be neutralized without being extracted by an organic solvent/aqueous solution. The product is supplied; or the operation of purifying by crystallization, column chromatography, or the like is carried out separately or in combination, and then provided as a product.

Among the phthalocyanine dyes represented by the above formula (2) obtained in the above manner, R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ are hydrogen, q ₅ The phthalocyanine compound represented by 2, q ₆ , q ₇ and q ₈ (for example, when t=u=v=w=1) usually becomes a mixture which is Ra(SO ₂ -Z ₅ ) as a mixture. The isomers at the respective substitution positions of Rb(SO ₂ -Z ₆ ), Rc(SO ₂ -Z ₇ ), and Rd(SO ₂ -Z ₈ ) are represented by the following formula (a)-1 to A mixture of compounds represented by (a)-4.

In other words, the compound represented by the above formula (a)-1 to (a)-4 is a β-position substitution type (when R ₁ to R ₁₆ in the following general formula (IV) are each set to 1 A phthalocyanine compound having a specific substituent at the 2 position and/or 3 position, 6 position and/or 7 position, 10 position and/or 11 position, 14 position and/or 15 position.

The phthalocyanine dye represented by the general formula (1) corresponds to an α-position substitution type (in 1 position and/or 4 position, 5 position and/or 8 position, 9 position and/or 12 position, 13 position and/or a phthalocyanine compound having a specific substituent at the 16-position, and a phthalocyanine dye represented by the formula (2) corresponds to a β-position substitution type (at 2 and/or 3, 6 and/or 7 positions) a phthalocyanine compound having a specific substituent at the 10th position and/or 11th position, 14th position and/or 15th position). In the present invention, in any of the substitution types, it is important to have a specific substituent represented by -SO-Z and/or -SO ₂ -Z for good fastness.

In the following, specific examples of the phthalocyanine dye represented by the general formula (1) or the general formula (2) are shown by the following general formula (IV), but the phthalocyanine dye used in the present invention is not limited to the following. example of.

(Illustration of a phthalocyanine dye represented by the general formula (1))

[Cyan ink composition]

The ink set of the present invention includes a cyan ink composition containing the phthalocyanine dye represented by the above formula (1) and the phthalocyanine dye represented by the above formula (2). By using the dye of the formula (1) of the α-position substitution type and the dye of the formula (2) of the β-position substitution type, the ratio adjustment of the α position to the β position in the molecule, rather than in the molecule, can be performed, As a result, good firmness and high print density can coexist.

In the cyan ink composition, the quality of the phthalocyanine dye represented by the general formula (1) and the phthalocyanine dye represented by the general formula (2) is preferably 50/50 to 10/90, more preferably 40/60. ~20/80. By setting the mass ratio of the dye to the above range, it is possible to obtain excellent characteristics such as temporal stability (viscosity change or precipitation) at a high concentration of the ink, and strong ozone of the printed sample using the ink. Excellent in performance and excellent in printing density.

Further, in the cyan ink composition, the content of the phthalocyanine dye represented by the formula (1) is preferably from 0.1% by mass to 10% by mass. When it is less than 0.1% by mass, the stability with time and the printing density at a high concentration of the ink are not good, and if it exceeds 10% by mass, the ozone solidity of the printed sample is lowered.

Furthermore, in the present invention, 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 colorant, and the cyan ink composition contains In the ink set of the phthalocyanine dye represented by the following general formula (1) and the phthalocyanine dye represented by the following general formula (2) as a coloring agent, the yellow ink composition shown below and The magenta ink composition can thereby obtain an image having an excellent color balance and is excellent in a fading balance, so that the image quality of the printed matter can be favorably maintained for a longer period of time.

(yellow)

Next, the coloring agent used in the yellow ink composition constituting the ink set of the present invention will be described.

In the ink set of the present invention, the coloring agent used in the yellow ink composition is not limited to the coloring agent of a specific structure, but is preferably light resistance of the ink composition of other colors. Ozone resistance and yellow ink composition light resistance. The difference between ozone resistance is small.

In view of the above, in the present invention, the yellow dye used as a colorant in the yellow ink composition is preferably selected from the group consisting of compounds represented by the following formula (Y) and formula (Y-2) and a compound in a group consisting of salts. Among them, the general formula (Y-2) does not contain the general formula (Y).

(In the general formula (Y), M each independently represents a hydrogen atom or a cation, and when M represents a cation, it means a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion or an NH ₄ ⁺ ion)

M represents a hydrogen atom, a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion or an NH ₄ ⁺ ion, and particularly preferably a Na ⁺ ion, a K ⁺ ion or an NH ₄ ⁺ ion, more preferably a Na ⁺ ion, a K ⁺ ion Among them, especially the K ⁺ ion. In the dye represented by the general formula (Y), the counter cation as the main component of M is preferably K ⁺ ion, and more preferably all M is K ⁺ ion.

The dye represented by the general formula (Y) may also be in a state in which a mixed salt of a plurality of M is present. When the dye represented by the general formula (Y) is a mixed salt, among the Ms of the dye represented by the general formula (Y) contained in the ink, the molar fraction is preferably 50%. ~100%, more preferably 80%~100% of M is K ⁺ ions, wherein particularly preferably 90% to 100% of M is K ⁺ ions. M other than the K ⁺ ion is preferably a Na ⁺ ion or an NH ₄ ⁺ ion, more preferably a Na ⁺ ion.

Further, it is preferable that the dye represented by the general formula (Y) is not a mixed salt, and M of all the dyes represented by the general formula (Y) contained in the ink is K ⁺ ions. The reason is that, by using all of M as K ⁺ ions, the carboxyl group or its salt (-CO ₂ M) which is an ionic hydrophilic group is dissociated and ionized into -CO in a state in which the molecules are dissolved in an aqueous solution or an ink solution. ₂ ^- and M ⁺ , and the cationic species are exchanged in this state, whereby the state in which the salt having a lower solubility in the aqueous solution or the ink solution is formed can be obtained, and the effect of precipitating the salt in the state of the coloring agent can be easily suppressed.

Among the compounds of the above formula (Y), a compound of the following formula (Y-1) is particularly preferably used.

Formula (Y-1)

In the formula (Y-2), R ₄ each independently represents a monovalent group, and R ₅ each independently represents -OR ₆ or -NHR ₇ , and R ₆ and R ₇ each independently represent a hydrogen atom or a monovalent group. X ₃ represents a divalent linking group, and n ₃ is 0 or 1, and Ar ₃ each independently represents a divalent heterocyclic group, and Ar ₄ each independently represents an alkyl group, an aryl group or a monovalent triazine ring group.

The general formula (Y-2) will be described.

(substituent)

First, the substituent in the formula (Y-2) will be described.

The substituent may be a group which may be substituted, and examples thereof 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, and a hydroxyl group. Nitro, carboxy (may also be a salt), alkoxy, aryloxy, nonyloxy, heterocyclic oxy, decyloxy, amine methoxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyl Oxyl, amine (including anilino), mercaptoamine, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, aminesulfonylamino, alkylsulfonylamino Or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo (also salt), alkylsulfinyl, arylsulfin Alkyl, alkylsulfonyl, arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, amidyl, fluorenylene, phosphino, phosphinyl, phosphinyloxy, A phosphinylamino group, a decyl group, and the like.

These substituents may be further substituted, and as a further substituent, a group selected from the substituents described above may be mentioned. Examples of the substituent having a further substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. . Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an ethenylaminosulfonyl group, and a benzhydrylaminosulfonyl group.

In the formula (Y-2), R ₄ represents a monovalent group, R ₅ represents -OR ₆ or -NHR ₇ , and R ₆ and R ₇ represent a hydrogen atom or a monovalent group.

Examples of the monovalent group represented by R ₄ , R ₆ and R ₇ 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, and a cyano group. , hydroxy, nitro, carboxy (may also be a salt), alkoxy, aryloxy, decyloxy, heterocyclic oxy, decyloxy, amine methoxycarbonyl, alkoxycarbonyloxy, aryloxy Alkoxycarbonyl group, amine group (including anilino group), mercaptoamine group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, aminesulfonylamino group, alkylsulfonyl group Amino or arylsulfonylamino, fluorenyl, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfo (also a salt), alkylsulfinyl, aryl Sulfonyl, alkylsulfonyl, arylsulfonyl, fluorenyl, aryloxycarbonyl, alkoxycarbonyl, amine carbaryl, quinone imine, phosphino, phosphinyl, phosphinyloxy A group, a phosphinylamino group, a decyl group, and the like.

The monovalent group represented by R ₄ , R ₆ and R ₇ will be described in more detail.

Examples of the halogen atom represented by R ₄ , R ₆ and R ₇ include a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkyl group. The alkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. Examples of the substituent include a group described in the above substituent, but a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (which may also be a salt form), and a carboxyl group are preferred. For the form of salt). Examples of the above alkyl group include methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, hydroxyethyl group, and cyanoethyl group. And 4-sulfobutyl group and the like.

The cycloalkyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted cycloalkyl group. The cycloalkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted cycloalkyl group having a carbon number of 5 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group.

The aralkyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted aralkyl group. The aralkyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above aralkyl group include a benzyl group and a 2-phenylethyl group.

The alkenyl group represented by R ₄ , R ₆ and R ₇ includes a linear, branched or cyclic substituted or unsubstituted alkenyl group. The alkenyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above alkenyl group include a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, a 2-cyclopenten-1-yl group, and a 2-cyclohexen-1-yl group. Wait.

The alkynyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkynyl group. The alkynyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the alkynyl group include an ethynyl group and a propargyl group.

The aryl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted aryl group. The aryl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the aryl group include a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecanylaminophenyl group, and the like.

The heterocyclic group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted heterocyclic group. The heterocyclic group represented by R ₄ , R ₆ and R ₇ is preferably one in which a hydrogen atom is removed from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound of 5 or 6 members. The monovalent group is preferably a 5-membered or 6-membered aromatic heterocyclic group having a carbon number of 3 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the heterocyclic group include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

The alkoxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkoxy group. The alkoxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.

The aryloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted aryloxy group. The aryloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxy group having a carbon number of 6 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, and a 4-tetradecylaminobenzene group. Oxyl and the like.

The decyloxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted decyloxy group. The decyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted decyloxy group having a carbon number of 3 to 20. Examples of the substituent include the groups described in the above substituents. Examples of the above decyloxy group include a trimethyldecyloxy group and a tert-butyldimethylsilyloxy group.

The heterocyclic oxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted heterocyclic oxy group. The heterocyclic oxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the heterocyclic oxy group include 1-phenyltetrazole-5-oxy group and 2-tetrahydropyranyloxy group.

The decyloxy group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted decyloxy group. The alkoxy group represented by R ₄ , R ₆ and R ₇ is preferably a methyl methoxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a carbon number of 6 to 30. A substituted or unsubstituted arylcarbonyloxy group. Examples of the substituent include the groups described in the above substituents. Examples of the above methoxyl group include a methyl methoxy group, an ethoxy group oxy group, a trimethyl ethoxy group oxy group, a stearyl oxy group, a benzyl methoxy group, and a p-methoxy phenyl carbonyl group. Wait.

The amine methyl methoxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted amine methyl methoxy group. The amine methyl methoxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted amine methyl methoxy group having a carbon number of 1 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above amine methyl methoxy group include N,N-dimethylamine methyl methoxy group, N,N-diethylamine methyl methoxy group, morpholinylcarbonyloxy group, N,N- Di-n-octylaminocarbonyl, N-n-octylamine, methyloxy, and the like.

The alkoxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a third butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

R _4, R ₆ and R ₇ aryloxycarbonyloxy group represented by comprising a substituted or unsubstituted aryloxycarbonyl group. The aryloxycarbonyloxy group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonyloxy group having a carbon number of 7 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a p-(n-hexadecyloxy)phenoxycarbonyloxy group.

The amine group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted amine group. The amine group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted carbon number of 6 to 30. Anilino group. Examples of the substituent include the groups described in the above substituents. Examples of the above amine group include an amine group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group.

The mercaptoamine group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted mercaptoamine group. The mercaptoamine group represented by R ₄ , R ₆ and R ₇ is preferably a mercaptoamine group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a carbon number of 6 ~30 substituted or unsubstituted arylcarbonylamino group. Examples of the substituent include the groups described in the above substituents. Examples of the above mercaptoamine group include a mercaptoamine group, an ethenylamino group, a trimethylethenylamino group, a laurylamine group, a benzhydrylamino group, and 3,4. 5-tri-n-octyloxyphenylcarbonylamino group and the like.

The aminocarbonylamino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted aminocarbonylamino group. The aminocarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above aminocarbonylamino group include an amine mercaptoamine group, an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, and a morpholinylcarbonylamino group. Wait.

The alkoxycarbonylamino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl group. A methoxycarbonylamino group or the like.

The aryloxycarbonylamino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the aryloxycarbonylamino group include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and a m-(n-octyloxy)phenoxycarbonylamino group.

The amine sulfonylamino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted sulfonylamino group. The aminesulfonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted sulfonylamino group having a carbon number of 0 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above aminesulfonylamino group include an aminesulfonylamino group, an N,N-dimethylaminosulfonylamino group, and an N-n-octylaminosulfonylamino group.

R _4, R ₆ alkylsulfonyl group and arylsulfonyl group or acyl group represented by R ₇ contains a substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group acyl group. The alkylsulfonylamino group or the arylsulfonylamino group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms. A substituted or unsubstituted arylsulfonylamino group having an amine group and a carbon number of 6 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the alkylsulfonylamino group or the arylsulfonylamino group include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, and 2,3. , 5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like.

The alkylthio group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkylthio group. Alkylthio group as R _4, R ₆ and R ₇ represented preferably by 1 to 30 substituted or unsubstituted alkylthio group having a carbon number. Examples of the substituent include the groups described in the above substituents. Examples of the above alkylthio group include a methylthio group, an ethylthio group, an n-hexadecylthio group and the like.

The arylthio group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted arylthio group. The arylthio group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted arylthio group having a carbon number of 6 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above arylthio group include a phenylthio group, a p-chlorophenylthio group, a m-methoxyphenylthio group and the like.

The heterocyclic thio group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted heterocyclic thio group. The heterocyclic thio group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above heterocyclic thio group include a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

The amine sulfonyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted sulfonamide group. The amine sulfonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted sulfonyl group having a carbon number of 0 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above amine sulfonyl group include N-ethylamine sulfonyl group, N-(3-dodecyloxypropyl)amine sulfonyl group, and N,N-dimethylamine sulfonyl group. And N-acetamidosulfonyl, N-benzhydrylsulfonyl, N-(N'-phenylaminecarbamyl)aminesulfonyl and the like.

The alkylsulfinyl or arylsulfinyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkylsulfinyl group or an arylsulfinyl group. The alkylsulfinyl group or the arylsulfinyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, A substituted or unsubstituted arylsulfinyl group having a carbon number of 6 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the above alkylsulfinyl group or arylsulfinyl group include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinium. Base.

The alkylsulfonyl or arylsulfonyl group represented by R ₄ , R ₆ and R ₇ includes a substituted or unsubstituted alkylsulfonyl group or an arylsulfonyl group. The alkylsulfonyl or arylsulfonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, and the carbon number is 6 to 30 substituted or unsubstituted arylsulfonyl groups. Examples of the substituent include the groups described in the above substituents. Examples of the alkylsulfonyl group or the arylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, and a p-methylphenylsulfonyl group.

The fluorenyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted fluorenyl group. The fluorenyl group represented by R ₄ , R ₆ and R ₇ is preferably a fluorenyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted group having 7 to 30 carbon atoms or An unsubstituted arylcarbonyl group, a substituted or unsubstituted heterocyclic carbonyl group having a carbon number bonded to a carbonyl group of 4 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above mercapto group include an ethyl fluorenyl group, a trimethylethyl fluorenyl group, a 2-chloroethyl fluorenyl group, a stearyl group, a benzamyl group, a p-(n-octyloxy)phenylcarbonyl group, and 2 a pyridylcarbonyl group, a 2-furylcarbonyl group or the like.

The aryloxycarbonyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted aryloxycarbonyl group having a carbon number of 7 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, a m-nitrophenoxycarbonyl group, and a p-(tert-butyl)phenoxycarbonyl group.

The alkoxycarbonyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, an n-octadecyloxycarbonyl group and the like.

The amine mercapto group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted amine carbenyl group. The amine forminyl group represented by R ₄ , R ₆ and R ₇ is preferably a substituted or unsubstituted amine carbenyl group having 1 to 30 carbon atoms. Examples of the substituent include the groups described in the above substituents. Examples of the above amine carbenyl group include an amine methyl sulfonyl group, an N-methylamine methyl fluorenyl group, an N,N-dimethylamine methyl fluorenyl group, and an N,N-di-n-octylamine hydrazine group. Base, N-(methylsulfonyl)amine, mercapto and the like.

The phosphino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted phosphino group. Preferably, R ₄ , R ₆ and R ₇ represent a substituted or unsubstituted phosphino group having a carbon number of 2 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the phosphine group include a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group and the like.

The phosphinyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted phosphinyl group. Preferably, R ₄ , R ₆ and R ₇ represent a substituted or unsubstituted phosphinyl group having a carbon number of 2 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the phosphinyl group include a phosphinyl group, a dioctyloxyphosphinyl group, and a diethoxyphosphinyl group.

The phosphinyloxy group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted phosphinyloxy group. Preferably, R ₄ , R ₆ and R ₇ represent a substituted or unsubstituted phosphinyloxy group having a carbon number of 2 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the phosphinyloxy group include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

The phosphinylamino group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted phosphinylamino group. Preferably, R ₄ , R ₆ and R ₇ represent a substituted or unsubstituted phosphinylamino group having a carbon number of 2 to 30. Examples of the substituent include the groups described in the above substituents. Examples of the phosphinylamino group include a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.

The fluorenyl group represented by R ₄ , R ₆ and R ₇ contains a substituted or unsubstituted fluorenyl group. A substituted or unsubstituted decyl group having a carbon number of 3 to 30 is preferred. Examples of the substituent include the groups described in the above substituents. Examples of the above fluorenylalkyl group include a trimethyldecyl group, a tert-butyldimethylsilyl group, and a phenyldimethylalkylene group.

In the formula (Y-2), R _{4 is} preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an alkyl group, and still more preferably a methyl group, an ethyl group, a propyl group, a n-butyl group or a third group. The base, and more preferably the third butyl group.

R _{5 is} preferably -NHR ₇ .

R ₆ and R _{7 are} preferably a hydrogen atom, an alkyl group, a decyl group, an alkylsulfonyl group or an arylsulfonyl group, more preferably a hydrogen atom, an alkyl group or a fluorenyl group, and particularly preferably a hydrogen atom.

In the formula (Y-2), X ₃ represents a divalent linking group. The divalent linking group represented by X ₃ may, for example, be an alkyl group (for example, a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group) or an alkenyl group (for example, a vinyl group). , propylene group), an alkynyl group (for example, an ethynyl group, a propynyl group), an aryl group (for example, a phenyl group, a naphthyl group), a divalent heterocyclic group (for example, 6-chloro-1,3) , 5-triazine-2,4-diyl, pyrimidine-2,4-diyl, quinoxaline-2,3-diyl), -O-, -CO-, -NR- (R is a hydrogen atom , alkyl or aryl), -S-, -SO ₂ -, -SO- or a combination of these.

The alkyl group, the alkenyl group, the alkynylene group, the aryl group, the divalent heterocyclic group, or the alkyl group or the aryl group represented by R may have a substituent. As an example of a substituent, it can be listed The group described in the above substituent is preferably a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (which may be in the form of a salt), and a carboxyl group (which may be in the form of a salt).

X _{3 is} preferably an alkylene group having 10 or less carbon atoms, an extended alkenyl group having 10 or less carbon atoms, an extended alkynyl group having 10 or less carbon atoms, and an extended aryl group having 6 or more and 10 or less carbon atoms. Divalent heterocyclic group, -O-, -S- or a combination of these.

The total carbon number of the divalent linking group represented by X ₃ is preferably from 0 to 50, more preferably from 0 to 30, most preferably from 0 to 10.

n ₃ is 0 or 1, preferably 1.

Ar ₃ represents a divalent heterocyclic group. As the hetero ring, a 5-membered ring or a 6-membered ring is preferred, and the rings may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring. Specific examples thereof include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, porphyrin, pyridazine, quinoxaline, pyrrole, indole, furan, and benzo. Furan, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, Benzoisoxazole, pyrrolidine, piperidine, piperazine, imidazolium, thiazoline and the like.

Among them, an aromatic heterocyclic group is preferred, and more preferred are pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzo. Isothiazole, thiadiazole, most preferably thiadiazole.

The divalent heterocyclic group represented by Ar ₃ may have a substituent, and examples of the substituent include the group described in the above substituent.

Ar ₄ represents an alkyl group, an aryl group or a monovalent triazine ring group.

The alkyl group and the aryl group represented by Ar ₄ have the same meanings as the alkyl group and the aryl group represented by R ₄ , R ₆ and R ₇ , and the preferred range is also the same.

As Ar ₄ , an aryl group or a monovalent triazine ring group is preferred, and an aryl group is more preferred, and a phenyl group is more preferred.

The alkyl group, the aryl group or the monovalent triazine ring group represented by Ar ₄ may further have a substituent. Examples of the substituent include the group described in the above substituent group, and among them, a sulfo group is preferred. Or carboxyl.

In the general formula (Y-2), a plurality of R ₄ , a plurality of R ₅ , a plurality of Ar ₄ and a plurality of Ar ₃ may be the same or different from each other.

A compound represented by the formula (Y-2) can be used as a yellow dye. Therefore, from the viewpoint of improving solubility, it is preferred to have an ionic hydrophilic group as R ₄ , R ₆ or R ₇ or an ionic hydrophilic group as R ₄ , R ₆ , R ₇ or Ar ₄ or The substituent possessed by Ar ₃ .

Here, the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphinium group, a quaternary ammonium group, and the like. The ionic hydrophilic group is preferably a carboxyl group, a phosphonium group or a sulfo group, and more preferably a carboxyl group or a sulfo group. The carboxyl group, the phosphonium group and the sulfo group may also be in the form of a salt, and examples of the counter ion forming a salt include an ammonium ion, an alkali metal ion (for example, a lithium ion, a sodium ion, a potassium ion), and an organic cation (for example, a tetramethylammonium ion). , tetramethylphosphonium ion, tetramethyl phosphonium). Among the counter ions, an alkali metal salt is preferred. Among the alkali metal salts, potassium ions, sodium ions, and lithium ions are preferred, and sodium ions and potassium ions are preferred.

In the general formula (Y-2), it is particularly preferred that Ar ₄ has an ionic hydrophilic group.

Specific examples of the dye represented by the general formula (Y-2) are shown below, but The invention is not limited to the specific examples.

The dye represented by the general formula (Y), the formula (Y-1), and the formula (Y-2) can be synthesized by a general synthesis method, for example, with [0066] of JP-A-2004-083903 and The method described in the same manner is synthesized in the same manner.

When a compound represented by the above formula (Y), formula (Y-1) and formula (Y-2) is used as a yellow dye, it is preferable to have 380 nm in an aqueous solution from the viewpoint of color reproducibility. The maximum absorption wavelength (λmax) of ~490nm, more preferably It has a λmax of 400 nm to 480 nm, and particularly preferably λmax of 420 nm to 460 nm.

Furthermore, in the present invention, in addition to the compound represented by the above formula (Y), formula (Y-1) or formula (Y-2), in order to adjust the color tone or the like of the yellow ink composition, Greatly impaired light resistance. In the range of ozone resistance, other yellow dyes are used in combination.

Examples of the yellow-based dye to be used together include CI Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 59, 68, 87, and 93. 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61 , 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, CI active yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, CI alkaline yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, etc., but are not limited to the dyes.

In the present invention, the content of the coloring agent in the yellow ink composition (in a total amount when a plurality of coloring agents are used) can be appropriately determined depending on the color value of the compound (dye) used as the coloring agent, but relative The total mass of the yellow ink composition is preferably 1.0% by mass to 6.0% by mass. By setting the content of the coloring agent in the yellow ink composition to 1.0% by mass or more, good color rendering properties can be obtained, and the content of the coloring agent can be made 6.0% by mass or less. Characteristics such as the discharge property of the nozzle required for the ink composition of the ink jet recording method become good Well, it prevents clogging of the ink nozzles.

In particular, the content of the compound represented by the above formula (Y), formula (Y-1) or formula (Y-2) or a salt thereof in the yellow ink composition is relatively higher than the total mass of the yellow ink composition. Preferably, it is 1.5% by mass to 5.5% by mass, more preferably 2.0% by mass to 5.5% by mass.

Light resistance of a dye as a compound represented by the above formula (Y), formula (Y-1) or formula (Y-2) or a salt thereof. Ozone resistance is very excellent, so by making the ink set combined with the black ink, cyan ink and magenta ink of the present invention, the light resistance of each color can be made. Ozone resistance is dramatically improved, even in light. After the ozone exposure test, the color balance of the image will not collapse, and the image quality can be maintained for a long time.

Further, in the yellow ink composition, a dye which is a compound represented by the above formula (Y), formula (Y-1) or formula (Y-2) or a salt thereof, and the above-mentioned invention are used together. A yellow-based dye (for example, CI Direct Yellow 58) can be used, which can be adjusted to a better color balance, and can maintain the image quality of the print better in a longer period of time.

(magenta)

Next, the coloring agent 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 coloring agent used in the magenta ink composition is not limited to the coloring agent of a specific structure, but is preferably light resistant to the ink composition of other colors. Ozone resistance and the lightfastness of magenta ink compositions. The difference between ozone resistance is small.

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

In the above formula (M-1), A _M represents a 5-membered heterocyclic group.

B ₁ and B ₂ represent _{-CR 13 =, - CR 14 =} , or either one represents a nitrogen atom, the other represents -CR ₁₃ = or -CR ₁₄ =.

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an amine. Mercapto, alkylsulfonyl, arylsulfonyl, or aminesulfonyl. Each group may further have a substituent. However, R ₁₁ and R _{12 are} not simultaneously a hydrogen atom.

G, R ₁₃ and R ₁₄ each independently represent 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 cyano group, a carboxyl group, an aminomethyl group, an alkoxy group. Carbonyl, aryloxycarbonyl, fluorenyl, hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminemethyloxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyl Alkoxy, alkyl or aryl or heterocyclic substituted amine, mercaptoamine, ureido, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl sulfonate Amidino or arylsulfonylamino, nitro, alkylthio, arylthio, alkylsulfonyl or arylsulfonyl, alkylsulfinyl or arylsulfinyl, Aminesulfonyl, heterocyclic thio, or ionic hydrophilic. Each group can be further substituted by the groups. Further, R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5-membered ring or a 6-membered ring. Among them, the general formula (M-1) has at least one ionic hydrophilic group.

Here, the ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphinium group, a quaternary ammonium group, and the like. The ionic hydrophilic group is preferably a carboxyl group, a phosphonium group or a sulfo group, and among them, a carboxyl group or a sulfo group is preferred. The carboxyl group, the phosphonium group and the sulfo group may also be in the form of a salt, and examples of the counter ion forming a salt include an ammonium ion, an alkali metal ion (for example, a lithium ion, a sodium ion, a potassium ion), and an organic cation (for example, a tetramethylammonium ion). , tetramethylphosphonium ion, tetramethyl phosphonium). Among the counter ions, an alkali metal salt is preferred. Among the alkali metal salts, potassium ions, sodium ions, and lithium ions are preferred, and sodium ions and potassium ions are preferred.

The general formula (M-1) will be described.

A _M represents a 5-membered heterocyclic group. Examples of the hetero atom of the 5-membered heterocyclic ring include N, O, and S. As A _M , a nitrogen-containing 5-membered heterocyclic ring is preferred, and an aliphatic ring, an aromatic ring or other heterocyclic ring may be condensed on the hetero ring. Examples of preferred heterocyclic rings of A _M 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 benzo compound. Isothiazole ring. Each heterocyclic group may further have a substituent. Among them, a heterocyclic ring represented by the following general formula (a) to the general formula (i) is preferred.

In the general formulae (a) to (i), Rm ₁ to Rm _{20 have} the same meanings as those of R ₁₃ and R ₁₄ in the formula (M-1).

Among the general formulae (a) to (i), preferred are (a) to (h), more preferably (a) to (e), (g), (h), and particularly preferably (a). .

Rm _{1 is} preferably an electron withdrawing group having a substituent constant σp value of 0.20 or more, more preferably a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, and thus more preferably It is preferably a cyano group, an alkylsulfonyl group or an arylsulfonyl group.

Rm _{2 is} preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or a fluorenyl group, more preferably an alkyl group, and still more preferably an alkyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 6 carbon atoms.

Rm _{3 is} preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aromatic group or a heterocyclic group, more preferably an aryl group or a heterocyclic group substituted with an electron-donating group, and more preferably a A heterocyclic group substituted with an electron-donating group (preferably, an electron withdrawing group having a substituent constant σp value of 0.20 or more). The heterocyclic ring is preferably a benzothiazole ring or a benzoxazole ring, more preferably a benzothiazole ring. Each of the above groups may further have a substituent.

Rm ₄ to Rm _{20 are} preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, an aminomethyl group, an alkoxycarbonyl group or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group or a heterocyclic group. .

In the general formula (M-1), B ₁ and B ₂ respectively represent -CR ₁₃ =, -CR ₁₄ =, or either of them represents a nitrogen atom, and the other represents -CR ₁₃ = or -CR ₁₄ =. From the viewpoint of exhibiting more excellent performance, it is preferable that B ₁ and B ₂ represent -CR ₁₃ = and -CR ₁₄ =, respectively.

R ₁₁ and R ₁₂ are each independently, preferably a hydrogen atom, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted a substituted fluorenyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, more preferably a hydrogen atom, a substituted aryl group or a substituted heterocyclic group, wherein Preferably, the aryl group is substituted with a substituted heterocyclic group. However, R ₁₁ and R _{12 are} not simultaneously a hydrogen atom. The substituted aryl group is preferably a substituted phenyl group, and examples of the substituent include an alkyl group (such as a methyl group, an ethyl group, an isopropyl group, and a tributyl group), a carboxyl group, and a sulfo group. Examples of the heterocyclic ring of the above substituted heterocyclic group 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 benzisothiazole. The ring is preferably a benzothiazole ring. The substituent of the above substituted heterocyclic group may, for example, be an alkyl group, a carboxyl group or a sulfo group, and is preferably a sulfo group.

G, R ₁₃ and R ₁₄ each independently represent 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 cyano group, a carboxyl group, an aminomethyl group, an alkoxy group. Carbonyl, aryloxycarbonyl, fluorenyl, hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminemethyloxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyl Alkoxy, alkyl or aryl or heterocyclic substituted amine, mercaptoamine, ureido, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkyl sulfonate Merylamino and arylsulfonylamino, nitro, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, Aminesulfonyl, heterocyclic thio, or ionic hydrophilic. Each group can be further substituted by the groups.

And a halogen atom represented by G, R ₁₃ or R ₁₄ , an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, an aminomethyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an anthracene group. Alkyl, alkoxy, aryloxy, decyloxy, decyloxy, amine methoxycarbonyl, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amine, decylamino Aminesulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino or arylsulfonylamino, alkylthio, arylthio, alkylsulfonyl The substituent described in the above substituent J can be exemplified as the arylsulfonyl group, the alkylsulfinyl group or the arylsulfinyl group, the aminesulfonyl group or the heterocyclic thio group.

G is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group, an alkyl group or an aromatic group. Or a heterocyclic group-substituted amine group, mercaptoamine group, urea group, aminesulfonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonyl group A mercaptoamine group, an alkylthio group, an arylthio group, a heterocyclic thio group or an ionic hydrophilic group. Base It was replaced.

More preferably, G is a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, an amino group substituted with an alkyl group or an aryl group or a heterocyclic group, or a mercaptoamine group. Among them, an amine group which is preferably a hydrogen atom, substituted with an aryl group or a heterocyclic group (here, as an aryl group, preferably a phenyl group), a mercaptoamine group, is preferably substituted with an aryl group having a substituent. Examples of the substituent include a halogen atom, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), an alkoxy group, and an ionic hydrophilic group. When having a plurality of substituents, the substituent They can be bonded to each other to form a ring).

R ₁₃ and R ₁₄ are each independently, and are preferably a hydrogen atom, an alkyl group, a cyano group, a carboxyl group, an amine formazan group or an alkoxycarbonyl group. Each group can be further substituted.

R ₁₃ and R _{14 are more} preferably a hydrogen atom, an alkyl group, a cyano group or a carboxyl group. Among them, R ₁₃ is preferably a hydrogen atom and R ₁₄ is an alkyl group. Particularly, R ₁₃ is a hydrogen atom, and R ₁₄ is methyl.

The combination which is particularly preferable as the compound represented by the general formula (M-1) is the following (i) to (iv).

(i) a heterocyclic ring represented by A _M , preferably 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 The benzisothiazole ring is more preferably a pyrazole ring, an imidazole ring, a triazole ring, a thiazole ring, an isothiazole ring or a thiadiazole ring, and among them, a pyrazole ring, a triazole ring, a thiazole ring, and an isothiazole are preferred. Ring, thiadiazole ring, preferably pyrazole ring.

(ii) Preferably, B ₁ and B ₂ respectively represent -CR ₁₃ =, -CR ₁₄ =, and more preferably R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), and R ₁₄ is a hydrogen atom. Or an alkyl group (B ₂ is an unsubstituted or alkyl-substituted carbon atom), and particularly preferably, R ₁₃ is a hydrogen atom (B ₁ is an unsubstituted carbon atom), and R ₁₄ is a methyl group (B _{2 )} Is a carbon atom substituted by a methyl group).

(iii) R ₁₁ and R ₁₂ are each independently, preferably 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 fluorenyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, more preferably a hydrogen atom, a substituted aryl group, a substituted heterocyclic group, Among them, a substituted aryl group, a substituted heterocyclic group, a sulfo group-substituted aryl group, and a sulfo group-substituted heterocyclic group are preferred, and a sulfo group-substituted phenyl group and a sulfo group are preferred. Benzothiazolyl.

(iv) G is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a hydroxyl group, an alkoxy group, an aryloxy group, a decyloxy group, a heterocyclic oxy group, or an alkane group. Alkenyl or aryl or heterocyclic substituted amine, mercaptoamine, ureido, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulfonylamino, An arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group or an ionic hydrophilic group, more preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group or an anthracene group An oxy group, an amino group substituted with an alkyl group or an aryl group or a heterocyclic group, a mercaptoamine group, and particularly preferably an amino group substituted with an aryl group or a heterocyclic group, a mercaptoamine group, more preferably The amine group substituted with an aryl group having a substituent is preferably an amine group substituted with a phenyl group having a substituent (methyl group, ethyl group, isopropyl group, sulfo group or the like).

With respect to the preferable combination of the substituents of the compound represented by the formula (M-1), at least one of the various substituents is preferably a compound of the above preferred group. More preferably, the compound having a more preferred substituent is a compound of the above preferred group, and most preferably a compound having a substituent of the above preferred group.

In the present invention, among the compounds represented by the above formula (M-1), a compound represented by the following formula (M-2) is preferred.

In the general formula _{(M-2), A M} , B 1, B 2, A M the meaning of R ₁₁ and R ₁₂ in the general formula (M-1) _{is, B 1, B 2, R} 11 and R ₁₂ the same.

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 total number of carbon atoms constituting the alkyl group is 3 or more, and these may be further substituted.

b, c, and d are independent, and the meaning is the same as that of R ₁₃ and R ₁₄ , and may be bonded to each other by a and b, or e and d to form a ring. Among them, the general formula (M-2) has at least one ionic hydrophilic group.

Of formula (M-2), the same meaning as A _M in the general formula (M-1) of A _M, the preferred embodiments are also the same.

B _1, B ₂ with the meaning of the general formula (M-1) of B _1, B ₂ identical, preferred examples are also the same.

R _11, R ₁₂ with the meaning of the general formula (M-1) is R _11, the same as R _12, preferred embodiments are also the same.

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

More preferably, a and e are each independently, preferably a methyl group, an ethyl group or an isopropyl group, and among them, an ethyl group, an isopropyl group, and particularly preferably a = b = an ethyl group or an isopropyl group are preferable.

b, c, and d are each independently, and have the same meanings as R ₁₃ and R ₁₄ in the above formula (M-1), and may be bonded to each other by a and b, or e and d to form a ring. Among them, the general formula (M-2) has at least one ionic hydrophilic group.

More preferably, 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 and a carboxyl group are preferred. Particularly, a combination of b and d is preferably a hydrogen atom and a sulfo group.

The combination which is particularly preferable as the compound represented by the general formula (M-2) is the following (i) to (iv).

Examples of heterocyclic same meaning as A _M (i) of the above general formula (M-1) of A _M, the preferred embodiments are also the same.

the same meaning as (ii) B ₁ and B ₂ in the general formula B (M-1) ₁ and B _2, preferred examples are also the same.

(iii) R _11, R ₁₂ with the meaning of the general formula (M-1) is R _11, R ₁₂ the same, the preferred embodiments are also the same.

(iv) a and e are preferably an alkyl group or a halogen atom, preferably when a and e When all of the alkyl groups are unsubstituted alkyl groups, the total number of carbon atoms of a and e is 3 or more (preferably 5 or less), and b, c, and d are each a hydrogen atom, a halogen atom, an alkyl group, and an ionic property. The hydrophilic group (preferably, each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an ionic hydrophilic group). More preferably, a and e are each independently, preferably a methyl group, an ethyl group or an isopropyl group, and among them, an ethyl group, an isopropyl group, and particularly preferably a = b = an ethyl group or an isopropyl group are preferable. Further, 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 and a carboxyl group are preferred. Particularly, a combination of b and d is preferably a hydrogen atom and a sulfo group.

With respect to the preferable combination of the substituents of the compound represented by the formula (M-2), at least one of the various substituents is preferably a compound of the above preferred group, and more preferably a plurality of substituents. The compound of the above preferred group is preferably a compound in which all the substituents are the above preferred groups.

In the present invention, among the compounds represented by the above formula (M-2), a compound represented by the following formula (M-3) is preferred.

In the general formula (M-3), Z ₁₁ represents an electron withdrawing group in which the substituent constant σp value of Hammett is 0.2 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 a fluorenyl group. The meanings of R ₁₁ , R ₁₂ , a, b, c, d and e are the same as those in the above formula (M-2). R _13, R meaning as R ₁₄ in the general formula (M-2) is _13, the same as R _14. 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 above groups of Z ₁₁ , Z ₁₂ and Q may further have a substituent. Among them, the general formula (M-3) has at least one ionic hydrophilic group.

In the general formula _{(M-3), R 13} , R ₁₄ the same meaning as in the general formula (M-1) is R _13, R _14, preferred embodiments are also the same.

R _11, R ₁₂ with the meaning of the general formula (M-1) is R _11, the same as R _12, preferred embodiments are also the same.

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

In the general formula (M-3), the electron withdrawing group of Z ₁₁ is a zestidine having a substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less.

Specific examples of the electron withdrawing group having a σp value of 0.2 or more include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphine oxime. , diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, sulfo, Sulfhydryl, sulfonyl, thiocyanate, thiocarbonyl, alkyl halide, halogenated alkoxy, halogenated aryloxy, alkyl halide, halogenated alkylthio, heterocyclic, halogen atom, An azo group, a selenocyanate group, and an aryl group substituted with another electron-withdrawing group having a σp value of 0.2 or more.

As Z ₁₁ , a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group or a halogen atom is preferred, and a cyano group, an alkylsulfonyl group or an arylsulfonyl group is more preferred. It is a cyano group.

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

In more detail, 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 other than the carbon atom of the substituent, and more preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the substituent which Z ₁₂ has include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.

Examples of the alkyl group represented by Z ₁₂ include a methyl group, an ethyl group, a butyl group, an isopropyl group, a tert-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, and 3- a sulfopropyl group and a 4-sulfobutyl group, wherein a methyl group, an ethyl group, an isopropyl group, a third butyl group, particularly preferably an isopropyl group, a third butyl group, and particularly preferably a third butyl group. base.

The cycloalkyl group represented by 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 other than the carbon atom of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group represented by Z ₁₂ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms other than the carbon atom of the substituent. Examples of the above substituent include an ionic hydrophilic group. Examples of the above aralkyl group include a benzyl group and a 2-phenylethyl group.

The aryl group represented by 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 other than the carbon atom of the substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, a decylamino group, an amine carbaryl group, an amine sulfonyl group, a sulfonylamino group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the aryl group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and a m-(3-sulfopropylamino)phenyl group.

The heterocyclic group represented by 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 a decylamino group, an amine carbaryl group, an amine sulfonyl group, a sulfonylamino group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the heterocyclic group include 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl and 2-furyl.

The fluorenyl group represented by Z ₁₂ includes a fluorenyl group having a substituent and an unsubstituted fluorenyl group. The fluorenyl group is preferably a fluorenyl group having 1 to 12 carbon atoms other than the carbon atom of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of sulfhydryl groups include ethenyl and benzhydryl groups.

In the 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 the above substituents may be further substituted. The details of these substituents are the same as those of the above R ₁₃ and R ₁₄ .

Q is preferably an aryl or heterocyclic group substituted with an electron-donating group. The electron withdrawing group which becomes a substituent of Q is a substituent constant σp value of Hammett of 0.2 or more, preferably 0.3. The above pull electron base. The upper limit of the σp value is preferably 1 or less.

Specific examples of the electron withdrawing group having a σp value of 0.2 or more have the same meanings as Z ₁₁ in the above formula (M-3).

More specifically, Q is preferably a heterocyclic group substituted with an electron-donating group, and among them, a sulfo group, a substituted or unsubstituted amine carbenyl group, a substituted or unsubstituted amine sulfonium group is preferred. The phenyloxazole ring, the benzothiazole ring, and especially the benzothiazole ring substituted with a sulfo group or a substituted amine sulfonyl group.

A particularly preferable combination of the compounds represented by the formula (M-3) is those including the following (i) to (vi).

(i) Z ₁₁ is a zethidine having a substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less. More preferably, as Z ₁₁ , a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or a halogen atom, and more preferably a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, wherein The best is cyano.

(ii) as Z ₁₂ , preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or a fluorenyl group, more preferably an alkyl group. Each substituent may be further substituted. In more detail, 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 other than the carbon atom 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, preferred are methyl, ethyl, butyl, isopropyl, tert-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4 - sulfobutyl group, particularly preferably isopropyl, tert-butyl, most preferably a third butyl group.

(iii) 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 above substituents may be further substituted. Further, Q is preferably an aryl group or a heterocyclic group substituted with an electron-donating group. The electron withdrawing group which becomes a substituent of Q is a zethidine having a substituent constant σp value of 0.2 or more, preferably 0.3 or more. The upper limit of the σp value is preferably 1 or less. More specifically, Q is preferably a heterocyclic group substituted with an electron-donating group, and among them, a sulfo group, a substituted or unsubstituted amine carbenyl group, a substituted or unsubstituted amine sulfonium group is preferred. The phenyloxazole ring, the benzothiazole ring, and especially the benzothiazole ring substituted with a sulfo group or a substituted amine sulfonyl group.

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

the same meaning as (V) R ₁₃ and R ₁₄ in the general formula (M-2) in R ₁₃ and R _14, preferred embodiments are also the same.

(vi) R _11, R ₁₂ with the meaning of the general formula (M-2) in R _11, R ₁₂ the same, the preferred embodiments are also the same.

With respect to the preferable combination of the substituents of the compound represented by the formula (M-3), at least one of the various substituents is preferably a compound of the above preferred group, and more preferably a plurality of substituents. The compound of the above preferred group is preferably a compound in which all the substituents are the above preferred groups.

The compound (azo dye) represented by the general formula (M-1), the general formula (M-2), and the general formula (M-3) has at least one (preferably three or more, 6) in its molecule. The following) ionic hydrophilic groups.

The ionic hydrophilic group includes a sulfo group, a carboxyl group, a phosphinium group, a quaternary ammonium group, and the like. The ionic hydrophilic group is preferably a carboxyl group, a phosphonium group or a sulfo group, and among them, a carboxyl group or a sulfo group is preferred. In particular, it is preferred that at least one is a sulfo group. The carboxyl group, the phosphonium group and the sulfo group may also be in the form of a salt, and examples of the counter ion forming a salt include an ammonium ion, an alkali metal ion (for example, a lithium ion, a sodium ion, a potassium ion), and an organic cation (for example, a tetramethylammonium ion). , tetramethylphosphonium ion, tetramethyl phosphonium). Among the counter ions, an alkali metal salt is preferred. Among the alkali metal salts, potassium ions, sodium ions, and lithium ions are preferred, and potassium ions are most preferred. In particular, from the viewpoint of improving solubility and suppressing Bronze in inkjet printing, it is preferable that the ionic hydrophilic group is a sulfo group and the counter ion is a combination of lithium ions.

The compound represented by the formula (M-1), the formula (M-2), and the formula (M-3) preferably has three or more and six or less ionic hydrophilic groups in the molecule. More preferably, it has three or more and six or less sulfo groups, and more preferably has three or more and five or less sulfo groups.

Specific examples of the compound represented by the general formula (M-1), the general formula (M-2), and the general formula (M-3) are shown below, but the compound used in the present invention is not limited to the following examples. .

The magenta ink composition of the present invention preferably contains at least one selected from the group consisting of a compound represented by the above formula (M-1), formula (M-2), and formula (M-3) and a salt thereof. Colorant.

In the ink set of the present invention, inks having different color densities, such as a rich magenta ink composition and a light magenta ink composition, may be contained as the magenta ink composition. When both the rich magenta ink composition and the light magenta ink composition are contained in the ink set, it is preferred that at least one of the two contains the general formula (M-1) and the general formula. (M-2), a compound of the formula (M-3) or a salt thereof as a colorant, more preferably a pale magenta ink composition containing a formula (M-1), a formula (M-2), a formula The compound of (M-3) or a salt thereof is used as a colorant. By improving the lightfastness of the pale magenta ink composition. Ozone resistance, which can improve the light fastness of the image of the whole recorded object. Ozone resistance. It is preferable that both the rich magenta ink composition and the light magenta ink composition contain the compound of the above formula (M-1), formula (M-2), or formula (M-3) or a salt thereof as a coloring Agent.

In the ink set of the present invention, the content of the magenta dye in the magenta ink composition may be according to the general formula (M-1), the general formula (M-2), and the general formula (M-3) used. The color value of the compound (dye) is appropriately determined. When only one type of magenta ink composition is contained in the ink set, it is generally preferred that the formula (M-1), formula (M-2), and formula (M-3) are in the magenta ink composition. The content of the compound or a salt thereof is from 2.0% by mass to 10% by mass. By setting the content of the dye in the magenta ink composition to 2.0% by mass or more, sufficient color rendering properties can be ensured as the ink, and the content is made 10% by mass or less as the inkjet. The ink composition of the recording method is easy to ensure the discharge property from the nozzle or to prevent clogging of the nozzle.

In addition, when the ink set contains the magenta ink composition and the light magenta ink composition, the content of the coloring agent in the pale magenta ink composition may be based on the formula (M-1) used as a colorant. The color value of the compound (dye) of the formula (M-2) and the formula (M-3) is appropriately selected, and the formula (M-1) and the formula (M- in the composition of the pale magenta ink are usually used. 2) The content of the compound of the formula (M-3) or a salt thereof is preferably from 0.5% by mass to 3.5% by mass, more preferably from 1.0% by mass to 3.0% by mass. borrow When the content of the dye in the pale magenta ink composition is 0.5% by mass or more, coloring property required for the composition of the pale magenta ink can be secured, and the content is set to 3.5% by mass or less. It is possible to reduce or prevent the graininess in the image of the recorded matter recorded using the light magenta ink composition.

In addition, when the ink set contains the magenta ink composition and the light magenta ink composition, the content of the coloring agent in the rich magenta ink composition may be based on the formula (M-1) used as a colorant. The color value of the compound (dye) of the general formula (M-2) and the general formula (M-3) is suitably selected, and the general formula (M-1) and the general formula (M- in the concentrated magenta ink composition are usually selected. 2) The content of the compound of the formula (M-3) or a salt thereof is preferably from 3% by mass to 10% by mass. By setting the content of the dye in the rich magenta ink composition to 3% by mass or more, the color rendering property required for the rich magenta ink composition can be secured, and the content is made 10% by mass or less. It is possible to reduce or prevent the grainy feeling in the image of the recorded matter recorded using the light magenta ink composition.

When the ink set contains a rich magenta ink composition and a light magenta ink composition, it is preferred to combine the content (% by mass) of the coloring agent contained in the pale magenta ink composition with the rich magenta ink. The ratio of the content (% by mass) of the coloring agent contained in the material is set to 1:2 to 1:8. By constituting the content of the coloring agent at such a ratio, the graininess of the image recorded using the ink compositions can be reduced. Further, by forming an ink composition in which the colorant ratio is the colorant ratio and the concentration of the colorant is in the above range, between the rich magenta ink composition and the light magenta ink composition A good color balance is achieved and the ink jet nozzle is blocked.

In the ink set of the present invention, the magenta ink composition, the rich magenta ink composition, or the light magenta ink composition is selected from the group consisting of the general formula (M-1) and the general formula (M-2). The content of the coloring agent in the group consisting of the compound represented by the formula (M-3) and a salt thereof is according to the formula (M-1), the formula (M-2), and the formula (M-3). The type of each substituent, the type of the solvent component, and the like are determined, and it is preferred to include the formula (M-1), the formula (M-2), and the formula (M-) contained in the ink composition. a dye of at least one of the compound and the salt thereof, and the total amount of all the colorants contained in the ink composition is 0.1% by mass to 10% by mass, more preferably, based on the total mass of the ink composition It is in the range of 0.5% by mass to 5% by mass. By setting the amount of the coloring agent in the ink composition to 0.1% by mass or more, color development or image density on the recording medium can be ensured, and the amount of the coloring agent in the ink composition can be set to 10 mass. Below %, it is easy to adjust the viscosity of the ink composition, and it is easy to ensure characteristics such as discharge reliability or clogging resistance.

The magenta ink composition, the rich magenta ink composition, or the light magenta ink composition of the ink set of the present invention is selected from the group consisting of the general formula (M-1) and the general formula (M-2). In addition to the dye in the group consisting of the compound represented by the formula (M-3) and a salt thereof, other magenta dyes may be used in combination. As the magenta dye which can be used in combination, for example, CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83 can be exemplified. , 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 , CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, CI Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254 , 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, CI Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, CI Reactive Violet 1. 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, CI Basic Red 12, 13, 14, 15, 18 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, CI Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, In addition to 25, 27, 28, 35, 37, 39, 40, 48, etc., a heterocyclic type or an open-chain active methylene compound having a phenol, a naphthol, an aniline or a pyrazine, etc., may be further exemplified. a heteroaryl azo dye or an aryl azo dye (hereinafter referred to as a compound represented by the formula (M-11)) as an even component (hereinafter referred to as a coupling agent component) For example, an azomethine dye having an open-chain type active methylene compound or the like as a coupler component; an anthrapyridone dye (hereinafter, a compound represented by the formula (M-12)) (for example, US2004/0239739A1) The compound of No. 20 in Table 1 described in the specification, or the compound (13) described in the manual of International Publication No. 04/104108, etc.).

General formula (M-11):

In the formula, Y represents an alkyl group having a carbon number of 1 to 4, an alkoxy group, or a phenyl group substituted with OH, SO ₃ H or COOM, or a naphthyl group. Further, B represents a hydrogen atom or a formula below.

In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms substituted by H, OH or COOH, and R ₂ represents a carbon number substituted by OH, OCH ₃ , OC ₂ H ₅ , SO ₃ M, COOM. ~4 alkyl, M represents H, Li, Na, K, ammonium, or an organic amine. R ₃ represents a substituent.

In the formula, Z represents a non-metal atomic group required for formation of a nitrogen-containing 5-membered heterocyclic ring to a 6-membered heterocyclic ring. 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 simultaneously represent 0. When m ₁ is 2 or more, a plurality of R _{1 's} may be the same or different from each other. When m ₂ is 2 or more, a plurality of R _{2 's} may be the same or different from each other. When m ₃ is 2 or more, a plurality of R _{3 's} may be the same or different. n represents an integer from 1 to 4. When n is 2 or more, the dye mother core can form a dimer, a trimer, or a tetramer via R ₁ , R ₂ , and R ₃ .

(ink composition)

In the above, the coloring agent used in each ink composition of the present invention and the coloring agent in the ink composition have been described. Hereinafter, other components contained in each ink composition will be described.

Each of the ink compositions in the present invention can be obtained by dissolving the above coloring agent (dye) in a suitable solvent. As the solvent for dissolving the colorant in each of the above ink compositions, water or a mixed liquid of water and a water-soluble organic solvent is preferably used as the main solvent. As the water, ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water or the like can be used. Further, from the viewpoint of long-term storage, it is preferred to use water subjected to various chemical sterilization treatments such as irradiation with ultraviolet rays or addition of hydrogen peroxide.

The content of water in each ink composition constituting the ink set of the present invention is preferably 40% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass based on the ink composition.

As described above, each ink composition in the present invention can dissolve water-soluble organic substances. The agent is used as a solvent together with water. The water-soluble organic solvent is preferably one having the ability to dissolve the dye, and preferably has a vapor pressure lower than that of pure water.

As the water-soluble organic solvent used in the present invention, for example, ethylene glycol, propylene glycol, butylene glycol, pentanediol, 1,3-hexanediol, 2-butene-1,4-diol, Polyols such as 2-methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, diethylene glycol, triethylene glycol, dipropylene glycol, acetone-acetone, etc., γ- Esters such as butyrolactone and triethyl phosphate, mercapto alcohol, tetrahydrofurfuryl alcohol, thiodiglycol, etc., but are not limited to these water-soluble organic solvents. By using a water-soluble organic solvent together with water as a solvent for the ink composition, the discharge stability of the ink composition from the ink head can be improved, and the viscosity of the ink composition can be easily reduced without substantially changing other characteristics. Adjustments.

Further, each of the ink compositions of the present invention may contain at least one humectant selected from the group consisting of saccharides. By including the humectant in the ink composition, when the ink composition is used in an inkjet recording method, it is possible to suppress evaporation of moisture from the ink to moisturize the ink. As the saccharide used in the present invention, maltitol, sorbitol, gluconolactone, maltose or the like is preferable. Further, the above water-soluble organic solvent may also function as a humectant.

In the ink composition, the above-mentioned water-soluble organic solvent and/or humectant may be contained in an amount of 5% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, particularly preferably 5% by mass to 20% by mass. . By setting the content of the water-soluble organic solvent and/or the humectant to 5% by mass or more, good moisturizing properties of the ink can be obtained, and the content of the water-soluble organic solvent and/or the humectant can be set to 50% by mass or less, and the viscosity of the ink composition can be adjusted to be preferable for the inkjet recording method. Viscosity.

The ink set of the present invention preferably contains a betaine compound as needed in each ink composition, and particularly preferably a betaine-type surfactant having an oil-soluble group.

The betaine compound which can be preferably used in the present invention is preferably a betaine-type surfactant having an interfacial activity, and the betaine compound described herein means both a cationic moiety and an anionic site in the molecule. compound of.

Examples of the cationic moiety include an amine nitrogen atom, a nitrogen atom of a heteroaromatic ring, a boron atom having four bonds with carbon, a phosphorus atom, and the like. Among them, an amine nitrogen atom or a nitrogen atom of a heteroaromatic ring is preferred. Among them, a nitrogen atom of four grades is particularly preferred.

Examples of the anionic site include a hydroxyl group, a sulfur group, a sulfonylamino group, a sulfo group, a carboxyl group, a quinone imine group, a phosphoric acid group, and a phosphonic acid group. Among them, a carboxyl group or a sulfo group is particularly preferred. The charge as a whole molecule may be any of a cation, an anion, and a neutral, and is preferably neutral.

As the betaine compound, a compound described in paragraphs 0033 to 0043 of JP-A-2005-298744, or a betaine compound described in JP-A-2006-56916 can be preferably used.

The preferred amount of the betaine compound to be added is not particularly limited, but is preferably 0.001% by mass to 50% by mass, and more preferably 0.01% by mass to 20% by mass in the ink composition. Further, two or more kinds of betaine compounds may be used in combination, and it is preferred to use a combination of the formula W-1, the formula W-2 or the formula W-3. The compound represented by the formula W-1, the formula W-2 or the formula W-3 is particularly preferably a compound containing R as an alkyl group having 14 carbon atoms. Further, when the compound is used, the compound having an alkyl group having 14 carbon atoms preferably has a purity (for example, can be measured by liquid chromatography-mass spectrometry (LC-Mass)) of 90% or more. The best is 95% or more, and the best is 98% or more.

In addition, when two or more types are used in combination, the maximum amount of the compound is used in a mass ratio of from 1 to 10,000 times based on the mass ratio.

In particular, in the present invention, it is preferable that the total mass of the inorganic ions mixed into the ink from the betaine compound (especially a betaine surfactant) or the like is suppressed to 2% by mass or less based on the total mass of the ink.

The inorganic ion described herein represents an inorganic ion of a counter ion of a dye, and is derived from an inorganic ion of an inorganic salt as an impurity contained in a betaine surfactant, and becomes an ionic component desorbed from an ion equivalent of a betaine compound. The inorganic ion of the counter ion, the inorganic ion introduced from the inorganic salt used for pH adjustment, and the sum of the inorganic ions introduced by the ink additive such as a chelating agent or a preservative. However, in the present invention, ammonium ions are treated as volatile compounds and are excluded from the inorganic ions.

The total amount of inorganic ions is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

For example, Cl ^- derived from NaCl, Na ₂ SO ₄ , and SO ₄ ^2- are 100 ppm, preferably 30 ppm, more preferably 10 ppm (for example, quantifiable by ion chromatography analysis) in terms of 20 wt% aq.

In order to minimize the amount of inorganic ions in the ink, various methods can be used. For example, the method described in Paragraph No. 32 and Paragraph No. 33 of JP-A-2004-285269 can be used.

First, a method of removing inorganic ions contained in a raw material (for example, a betaine compound) used for ink when synthesizing a raw material can be cited. In the case of a water-soluble ink raw material, a large amount of ion-dissociable groups are often introduced for the purpose of improving water solubility. At this time, a large amount of inorganic substances are contained in the synthesis of the raw materials, or inorganic ions are necessarily contained as the counter ions. In order to remove the former ions, a desalination purification method by an electrolytic dialysis method using an ion selective permeable membrane, a method using an ion exchange resin, a desalting purification by a gel filtration method, or the like can be performed.

Further, a method of actively performing ion exchange during synthesis can also be used. For example, a method of exchanging excess ammonia or an organic amine to exchange with a metal ion, or a method of exchanging with an organic carboxylic acid in the case of an anion may be mentioned. Further, as the desalination method at the time of synthesis, a method in which a salt is actively precipitated by an organic solvent and removed by filtration can also be used.

Second, it is also preferable to carry out the desalination purification in a state of an ink material, that is, a concentrated aqueous solution (ink stock solution) obtained by dissolving various raw materials in a solvent such as water. Sometimes, desalting purification can also be carried out in the finished ink.

The ink used in the ink set of the present invention is an ink obtained by dissolving or dispersing a dye in water and a water-soluble organic solvent. Among them, an aqueous solution type ink using a water-soluble dye is preferred. Further, in the ink set, the ink having a betaine compound may be an ink of any color, and in particular, since it has a betaine compound, a colorless ink may be prepared.

In the case where the betaine compound of the present invention is used, bubbles may be generated in the ink. This bubble sometimes causes a printing defect in the ink jet recording, so that the problem can be solved by adding a compound (=antifoaming agent) having an action of eliminating bubbles in the ink.

As the antifoaming agent, various antifoaming agents such as a Pluronic defoaming agent (polyoxyethylene-polyoxypropylene type antifoaming agent) or an anthrone type defoaming agent can be used.

In the ink set of the present invention, it is preferred that the cyan ink composition and/or the magenta ink composition contain at least one selected from the group consisting of a naphthalene aromatic compound having a carboxyl group at the 2-position or a salt thereof. By adding at least one selected from the group consisting of naphthalene aromatic compounds having a carboxyl group at the 2-position or a salt thereof, the occurrence of a bronze color of the cyan ink composition can be prevented, and magenta can be enhanced. The moisture resistance of the ink composition. The above-described bronze color phenomenon is generally known as a phenomenon in which an ink composition containing a cyan dye is used for stereoscopic printing on an inkjet recording medium (particularly, a gloss recording medium). ) High-performance printed parts can be seen in red. In the case where a bronze phenomenon occurs, the color balance of the entire image becomes uneven and the image quality is lowered, so that a good image cannot be obtained.

The tetralin-based aromatic compound having a carboxyl group at the 2-position which is used in the present invention is particularly preferably an alkali metal salt of a naphthalene-based aromatic compound having a carboxyl group at the 2-position. Further, among the above alkali metal salts, a lithium salt is particularly preferably used. In the case where a lithium salt is used, the following effects can be obtained: not only the occurrence of the above-described bronze color phenomenon but also clogging of the ink jet nozzle can be prevented.

The naphthalene aromatic compound having a carboxyl group at the 2-position or a salt thereof may, for example, be 2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid or 6-hydroxy-2- Naphthoic acid, 4-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic 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, and 6-propoxy-2-naphthoic acid, and the like, and salts thereof, particularly lithium salts. Particularly preferred is 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 to the ink in the form of a salt or a naphthalene having a carboxyl group at the 2-position may be used. Any of the methods of adding an aromatic compound and a base capable of forming a salt thereto to the ink composition, respectively. Further, in the present invention, at least one selected from the group consisting of a naphthalene aromatic compound having a carboxyl group at the 2-position and a salt thereof may be used, and a naphthalene aromatic group having a carboxyl group at the 2-position may be used in combination. Both a compound and its salt.

When the above-mentioned cyan ink composition and/or magenta ink composition of the present invention is added to the group consisting of a naphthalene aromatic compound having a carboxyl group at the 2-position and a salt thereof (hereinafter, referred to as 2 positions) When at least one of the naphthalene-based aromatic compound having a carboxyl group is used, the ink composition preferably contains 0.1% by mass to 10% by mass of the naphthalene having a carboxyl group at the 2-position in terms of the total amount of the ink composition. An aromatic compound or the like is more preferably contained in an amount of 0.5% by mass to 5% by mass of a naphthalene aromatic compound having a carboxyl group at the 2-position. The amount of the naphthalene-based aromatic compound having a carboxyl group at the 2-position contained in the ink composition can be determined according to the type of the dye, the type of the dye contained in the ink composition, and the type of the solvent used in the ink composition. Wait, It is appropriate to determine the preferred amount.

When a naphthalene aromatic compound having a carboxyl group at the 2-position is added to the cyan ink composition, the amount (% by mass) of the cyan dye contained in the ink composition and the naphthalene aromatic having a carboxyl group at the 2-position The amount (% by mass) of the compound or the like is preferably from 1:0.1 to 1:10, more preferably from 1:0.3 to 1:6. When the content of the cyan dye in the cyan ink composition is 1, the content of the naphthalene aromatic carboxylic acid having a carboxyl group at the 2-position is more than 0.1, whereby the occurrence of a bronze color phenomenon can be reduced, and further By making the content of the naphthalene-based aromatic compound or the like having a carboxyl group at the 2-position less than 10, clogging of the ink-jet nozzle can be prevented.

On the other hand, when a naphthalene aromatic compound or the like having a carboxyl group at the 2-position is added to the magenta ink composition, the amount (% by mass) of the magenta dye contained in the ink composition is in the position of 2 The amount (% by mass) of the naphthalene-based aromatic compound having a carboxyl group is preferably from 1:0.5 to 1:10, more preferably from 1:1 to 1:6. When the content of the magenta dye in the magenta ink composition is 1, the content of the naphthalene aromatic compound having a carboxyl group at the 2-position is more than 0.5, thereby reducing the environment in a high-humidity environment. In the image quality deterioration caused by the bleed out of the image, the content of the naphthalene aromatic compound having a carboxyl group at the 2-position is less than 10, whereby clogging of the ink-jet nozzle can be prevented.

The ink composition constituting the ink set of the present invention preferably contains a nonionic surfactant. By adding a nonionic surfactant, the ink composition is excellent in permeability to a recording medium, and the ink composition can be quickly fixed to a recording medium at the time of printing. Further, it is preferably recorded by the ink composition One dot on the recording medium is as close as possible to a true circle, but by including a nonionic surfactant in the ink composition, the following effect can be obtained: the true circle of the image formed by one dot can be improved Degree, and can improve the image quality of the obtained image.

The nonionic surfactant used in the present invention is, for example, preferably an acetylene glycol surfactant, but is not limited thereto.

As the acetylene glycol-based surfactant, for example, Surfynol 465 (trademark), Surfynol 104 PG50 (trademark) (trade name, manufactured by Air Products and Chemicals Inc.), Olfine PD001 (trademark) can be exemplified. And Olfine E1010 (trademark) (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), preferably at least one selected from the above-mentioned products is added to the ink composition constituting the ink set of the present invention.

In the present invention, the nonionic surfactant is preferably contained in the ink composition in a form of preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 2% by mass of the nonionic surfactant. It is preferred to add to the ink composition. By including 0.1% by mass or more of the nonionic surfactant in the ink composition, the permeability of each ink composition to the recording medium can be improved. In addition, by setting the content of the nonionic surfactant in the ink composition to 5% by mass or less, it is possible to obtain an effect that the image formed on the recording medium by the ink composition is less likely to bleed out.

Further, in addition to the ion-based surfactant, glycol ethers are added as a penetration enhancer to the ink composition, whereby the permeability of the ink composition to the recording medium is improved, and when color printing is performed, adjacent At the boundary between the color inks, the bleeding of the ink is reduced, and a very clear image can be obtained. Therefore, it is preferred to add a penetration enhancer to the ink composition constituting the ink set of the present invention.

The above glycol ethers used as the permeation enhancer in the present invention are preferably ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol single. Ethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, etc., but not limited to these glycol ethers. The glycol ethers are preferably contained in the ink composition in an amount of from 3% by mass to 30% by mass, more preferably from 5% by mass to 15% by mass. By setting the amount of the glycol ether to be 3% by mass or more, it is possible to effectively prevent bleeding between adjacent inks during color printing, and further, the amount of addition is 30% by mass or less. Moreover, it is possible to easily prevent the occurrence of bleeding of the image and to improve the storage stability of the ink.

Further, in the ink composition of the present invention, a pH adjuster such as triethanolamine or an alkali metal hydroxide, a water-soluble polymer such as sodium alginate, a water-soluble resin, or a fluorine-based surfactant may be added as needed. Preservatives, anti-fungal agents, rust inhibitors, dissolution aids, antioxidants, and UV absorbers. These components may be used singly or in combination of two or more kinds. In addition, if it is not necessary to add, it may not be added. Those skilled in the art can use the selected preferred additives in preferred amounts within the scope of the effects of the present invention. Further, the above-mentioned dissolution aid refers to an additive which is used to dissolve the insoluble matter and to keep the ink composition as a uniform solution when the insoluble matter is precipitated from the ink composition.

Examples of the dissolution aid include pyrrolidone such as N-methyl-2-pyrrolidone and 2-pyrrolidone, and urea such as urea, thiourea or tetramethylurea, and allophanate. Examples are allophanates such as methyl alloformate, biurets such as biuret, dimethyl biuret, and tetramethyl biuret, but are not limited to these examples. Further, examples of the antioxidant include L-ascorbic acid and salts thereof, but are not limited thereto.

As the above-mentioned preservative or antifungal agent, for example, sodium benzoate, sodium pentachlorophenolate, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazole can be exemplified. Oral-3-one (PROXEL CRL, PROXEL BDN, PROXEL GXL, PROXEL XL2, and PROXEL TN (trade name)) of Avecia, etc., but is not limited to these examples.

Examples of the pH adjuster include amines such as diethanolamine, triethanolamine, propanolamine, and morpholine, and modified substances thereof, metal hydroxides such as potassium hydroxide, sodium hydroxide, and lithium hydroxide, and ammonium hydroxide. An ammonium salt such as a quaternary ammonium hydroxide (such as tetramethylammonium), a carbonate such as potassium carbonate, sodium carbonate or lithium carbonate, or other phosphates, but is not limited to these examples.

The ink composition constituting the ink set of the present invention is prepared by containing a component selected from the above components, and the viscosity of the obtained ink composition is preferably less than 10 mPa at 20 ° C. s. Further, the surface tension of the ink composition in the present invention is preferably 45 mN/m or less, and particularly preferably 25 mN/m to 45 mN/m at 20 °C. By adjusting the viscosity and the surface tension in this manner, an ink composition having characteristics preferable for the ink jet recording method can be obtained. The adjustment of the viscosity and the surface tension can be carried out by appropriately adjusting and selecting the solvent contained in the ink composition, the amount of addition of various additives, and the types thereof.

Further, the pH of the ink composition constituting the ink set of the present invention at 20 ° C is preferably 7.0 to 10.5, more preferably 7.5 to 10.0. By setting the pH of the ink composition at 20 ° C to 7.0 or more, it is possible to prevent the eutectoid plating layer of the ink jet head from being peeled off, and to stabilize the discharge characteristics of the ink composition from the ink jet head. In addition, by setting the pH of the ink composition to 10.5 or less at 20 ° C, it is possible to prevent various members which are in contact with the ink composition, for example, members constituting the ink cartridge or the ink jet head from deteriorating.

As a method of preparing the ink composition of the present invention, for example, a method of sufficiently mixing the various components contained in the ink composition and dissolving as uniformly as possible is carried out, and then filtering with a membrane having a pore diameter of 0.8 μm. The method of performing pressure filtration and further degassing the obtained solution using a vacuum pump is not limited to this method.

[ink 匣, inkjet printer]

The ink set of the present invention can be used as an ink cartridge in which the ink sets are integrally or independently accommodated, and is also preferable in terms of convenience in handling and the like. An ink cartridge comprising an ink jacket is well known in the art, and a known method can be used to produce an ink cartridge.

Further, the ink jet printer of the present invention comprises the above ink cartridge.

The ink set or ink cartridge of the present invention can be used for general writing instruments, recording instruments, pen plotters, etc., and is particularly preferably used for an ink jet recording method.

[Inkjet recording method]

An ink jet recording method in which the ink set or ink cartridge of the present invention can be used includes ink The water composition is ejected as a droplet from a fine nozzle and attaches the droplet to any recording method on the 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 electrostatic attraction. The electrostatic attraction method is a method in which a strong electric field is applied between a nozzle and an acceleration electrode disposed in front of the nozzle, and droplet-shaped ink is continuously ejected from the nozzle during a period in which the ink droplet passes between the deflection electrodes. Providing the printing information signal to the deflecting electrode, thereby causing the ink droplet to fly onto the recording medium and fixing the ink to the recording medium to record the image; or not biasing the ink droplet, and causing the ink droplet to be directed from the nozzle according to the printing information signal The ejection is recorded on the recording medium, whereby the image is fixed and recorded on the recording medium. The ink set or ink cartridge of the present invention is preferably a recording method for utilizing the electrostatic attraction method.

The second method is a method in which a pressure is applied to the ink liquid by a small pump, and the ink jet nozzle is mechanically vibrated by a quartz oscillator or the like, thereby forcibly ejecting the ink droplet from the nozzle. And a method in which the ink droplet ejected from the nozzle is charged while being ejected, and the printing information signal is supplied to the deflecting electrode to fly the ink droplet onto the recording medium while the ink droplet passes between the deflecting electrodes. Thereby an image is recorded on the recording medium. The ink set or ink cartridge of the present invention is also preferably used in the recording method.

The third method is a method in which a pressure and a printing information signal are simultaneously applied to the ink liquid by the piezoelectric element, so that the ink droplet is ejected from the nozzle to the recording medium, and an image is recorded on the recording medium. The ink set or ink cartridge of the present invention is used for the record The recording method is also preferred.

The fourth method is a method of foaming the ink liquid by using a minute electrode according to the printed signal information, and expanding the bubble, thereby ejecting the ink liquid from the nozzle to the recording medium to the recording medium. Record the image on it. The ink set or ink cartridge of the present invention is also preferably used in the recording method.

The ink set or the ink cartridge of the present invention is particularly preferable as an ink recording method using an ink jet recording method including the above four methods, and an ink composition used for recording an image on a recording medium.

[recorded matter]

The recorded matter recorded by using the ink set of the present invention has an excellent image quality with good color balance, and is excellent in light resistance and ozone resistance.

Example

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

(synthesis example)

Hereinafter, the preparation method of the dye mixture of the present invention will be described in detail in the examples, but the present invention is not limited to these examples.

The dye BLACK-11 used in the present invention can be derived, for example, according to the following synthetic route.

[Synthesis Example 1]

The synthesis flow of BLACK-11 is shown below.

(1) Synthesis of intermediate (B-5):

Add 8.5 mg of aminoacetophenone (a-2), 4.9 g of malononitrile, toluene at room temperature After 26.5 mL, 5.0 g of ammonium acetate, and 5.9 g of acetic acid, the internal temperature was raised to 100 ° C and stirred at the same temperature for 3 hours. After cooling the reaction liquid to 40 ° C, 31.8 mL of methanol was added, and after stirring for 20 minutes, the reaction liquid was filtered. It was washed with 42.4 mL of isopropyl alcohol and dried at 60 ° C for 8 hours. (B-5) 11.1 g was obtained.

(2) Synthesis of intermediate (C-5):

(B-5) 8.0 g, sulfur 2.8 g, sodium hydrogencarbonate 7.4 g, dimethylacetamide 160 mL, acetonitrile 80 mL, and water 80 mL were mixed, and the internal temperature was raised to 40 ° C, and Stir at the same temperature for 1 hour. After cooling the reaction liquid to 25 ° C, the insoluble matter was filtered to obtain (C-5) in a solution state.

(3) Synthesis of intermediate (T-1):

After 100 mL of acetone was cooled to an internal temperature of 0 ° C, 18.4 g of cyanuric chloride was added. Then, 27.5 g of aniline 2,5-disulfoaniline and 10.6 g of sodium carbonate were dissolved in 95 g of water, and the mixture was added dropwise at an internal temperature of 0 ° C to 4 ° C for 30 minutes. After stirring at an internal temperature of 0 ° C to 5 ° C for 2.5 hours, 200 mL of methanol and 200 mL of isopropyl alcohol were added dropwise at an internal temperature of 5 ° C or lower, and the precipitated insoluble matter was filtered to obtain a solution of (T-1). Status is obtained.

(4) Synthesis of intermediate (T-2):

In the state in which (T-1) obtained in the above Synthesis Example 1-(3) was maintained at an internal temperature of 20 ° C, (C-5) 240.0 g was added dropwise. After the dropwise addition, the internal temperature was raised to 30 ° C and stirred for 2.0 hours. After 2.3 L of isopropanol was added dropwise at an internal temperature of 30 ° C to 35 ° C for 1 hour, the mixture was stirred at the same temperature for 30 minutes. The reaction liquid was filtered, washed with isopropyl alcohol, and dried to obtain (T-2) 24.0 g.

(5) Synthesis of intermediate (T-3):

8.0 g of taurine and 6.8 g of sodium carbonate were completely dissolved in 650 mL of water at room temperature, and then (T-2) 24.0 g was added as a powder to the solution. The internal temperature was raised to 100 ° C and stirred at the same temperature for 1.5 hours. The reaction liquid was cooled to 25 ° C, and an intermediate (T-3) was obtained in a solution state.

(6) Synthesis of intermediate (f-6):

58 mL of water was added to 4.4 g of 2-aminobenzonitrile (e-1), and the mixture was stirred at room temperature, and 10.5 mL of 12 M hydrochloric acid water was added dropwise thereto, and the reaction liquid was cooled to an internal temperature of 0 °C. While maintaining the internal temperature at 0 ° C to 4 ° C, a 25% aqueous solution of 2.8 g of sodium nitrite was added dropwise thereto, and the mixture was stirred at an internal temperature of 0 ° C to 5 ° C for 1.5 hours. Thereafter, 0.4 g of urea was added and stirred for 15 minutes to obtain a diazonium salt solution. In addition to the above diazonium salt solution, 300 mL of water was added to the intermediate (T-3), and after cooling the internal temperature to 2 ° C, the previously prepared mixture was added dropwise at an internal temperature of 2 ° C to 4 ° C for 15 minutes. Diazonium salt solution. After the internal temperature was maintained at 2 ° C to 4 ° C and stirred for 2 hours, (f-6) was obtained in a solution state.

(7) Synthesis of BLACK-11:

(f-6) obtained in the above Synthesis Example 1-(6) was stirred at room temperature, and 17.7 g of the intermediate (G) was completely dissolved in 60 mL of water, followed by dropwise addition. 4.5 g of isoamyl nitrite was added dropwise at an internal temperature of 22 ° C, and stirred at the same temperature for 30 minutes. Thereafter, 0.2 g of isoamyl nitrite was further added dropwise, and the mixture was stirred at an internal temperature of 22 ° C for 2 hours. After the reaction liquid was subjected to dust filtration and removal of the insoluble matter, 183 mL of dimethylacetamide was added to the reaction liquid, and 1.1 L of isopropanol was added dropwise over 30 minutes. The slurry-like reaction liquid was filtered, and then washed with 2 L of methanol to obtain crude (BLACK-11).

To the crude body, 220 mL of water was added to dissolve, and then 370 mL of isopropyl alcohol was added dropwise and filtered again to obtain a wet cake. The wet cake was completely dissolved in 220 mL of water, and a 1 N-aqueous lithium hydroxide solution was added thereto to adjust the pH to 8.3 (25 ° C), and then 100 mL of methanol was added thereto to carry out dust filtration. The solution was heated to an internal temperature of 40 ° C, and 300 mL of a saturated lithium chloride-isopropanol solution was added dropwise at the same temperature, and the precipitated crystals were filtered to obtain a wet crystal. 170 mL of water and 100 mL of methanol were added to the obtained wet crystals, and 430 mL of a saturated lithium chloride-isopropanol solution was added dropwise while stirring at an internal temperature of 40 ° C, and the precipitated crystals were collected by filtration. After washing with 500 mL of isopropyl alcohol, it was dried at 40 ° C for 12 hours to obtain 11.3 g of fine (BLACK-11) M:Li/Na≒70/30 (mol/mol).

In addition, for BLACK-11 (M:Li/Na≒70/30 (mol/mol)) obtained in the above manner, a lithium salt type ion exchange resin (manufactured by Organo Co., Ltd.) was used, and IR-120B was changed. Li type) to obtain BLACK-11 (M: Li (ie, M is Li)).

[Synthesis Example 2]

The synthesis flow of BLACK-32 (M: Li) is shown below.

(1) Synthesis of intermediate (B-11):

40 g of a raw material (A-11; Wako Pure Chemicals) was added to 12.5 g of thiourea and 120 ml of water, and the mixture was stirred at 70 ° C for 5 hours. Filtration of the precipitated crystals, adding 5% NaOH 400 ml of the solution was stirred at room temperature for 3 hours, and then filtered to obtain 35.5 g of a yellow crystal of intermediate (B-11).

(2) Synthesis of intermediate (C-11):

57.0 g of reduced iron, 5.0 g of ammonium chloride, 35 ml of water, and 250 ml of isopropyl alcohol were refluxed for 30 minutes, and then 22.0 g of an intermediate (B-11) was added thereto, followed by reflux stirring for 1 hour. After filtration, concentration was carried out to obtain 15.0 g of yellow crystals of Intermediate (C-11).

(3) Synthesis of intermediate (D-11)

9.6 g of the intermediate (C-11) was added to 125 mL of acetone, and the mixture was stirred at an internal temperature of 50 ° C to be dissolved. After cooling the internal temperature to 4 ° C in an ice bath, 5.6 g of acetic anhydride was added dropwise over 15 minutes. After warming to room temperature, 50 mL of water was added, and acetone was distilled off under reduced pressure. After crystallization was collected by filtration, it was washed twice with 50 mL of water, and then dried at 80 ° C for 6 hours to obtain 9.9 g of white crystals of intermediate (D-11).

(4) Synthesis of intermediate (F-11)

4.3 g of the intermediate (E-11) was added to 43 mL of water and stirred at room temperature. After dropwise adding 4.0 mL of 12N hydrochloric acid, the internal temperature was cooled to 4 °C. 3 mL of an aqueous solution of 0.9 g of sodium nitrite was added dropwise thereto, and the mixture was stirred at 5 ° C or lower for 2 hours. Thereafter, 0.1 g of urea was added and stirred at an internal temperature of 4 ° C for 15 minutes to obtain a diazo solution. Further, 2.4 g of the intermediate (D-11) and 8.6 g of lithium acetate were dissolved in 55 mL of methanol and 3.5 mL of dimethylacetamide, and then the internal temperature was cooled to 5 ° C or lower. The diazo solution was added dropwise over 5 minutes at an internal temperature of 5 ° C or less. After stirring for 1.5 hours, 15.0 g of lithium chloride was added, followed by dropwise addition of 150 mL of isopropyl alcohol. Isopropanol 100 after filtration and crystallization The mL is cleaned. After drying at 80 ° C, 5.4 g of a brown crystal of the intermediate (F-11) was obtained.

(5) Synthesis of BLACK-32

The solution of 5.0 g of intermediate (F-11), 3.8 g of intermediate (G) and 50 mL of water was adjusted to pH 2 or lower by using 12N hydrochloric acid, and then isopentyl nitrite was added dropwise at an internal temperature of 35 ° C to 40 ° C. Ester 1.5g. After stirring at an internal temperature of 40 ° C for 4 hours, 20 g of lithium chloride was added, followed by dropwise addition of 25 mL of isopropyl alcohol. The internal temperature was cooled to 25 ° C, and the crystals were collected by filtration, and then washed with 50 mL of isopropyl alcohol. 60 mL of water was added to the crystal, and the internal temperature was raised to 40 ° C, and then 100 mL of isopropyl alcohol was added dropwise. After cooling the internal temperature to 25 ° C, the crystals were collected by filtration. The obtained crystal was added to 35 mL of water, and a 4 M aqueous lithium hydroxide solution was added so that the pH became 8.3. To the solution, 250 mL of isopropyl alcohol was added dropwise, and the precipitated crystals were collected by filtration. After washing with 30 mL of isopropyl alcohol, it was dried at 80 ° C to obtain 2.7 g of black crystals of (BLACK-32) (M:Li).

[Synthesis Example 3]

The synthesis flow of BLACK-31 (M: Li) is shown below.

(1) Synthesis of intermediate (B-12):

20.3 g of aminoacetophenone (A-12; finished product of Tokyo Chemical Co., Ltd.) was added to 150 mL of acetonitrile, and stirred at room temperature to completely dissolve it. Then, 13.4 mL of pyridine was added, and the internal temperature was maintained at 4 ° C under an ice bath. Adding 11.8 g of acetic anhydride dropwise, and Stir for 15 minutes at an internal temperature of 4 °C. 300 mL of water was added to the reaction liquid, followed by the addition of 5 mL of 12N hydrochloric acid, followed by filtration of crystals. The crystal was washed with 100 mL of water, and then dried at 80 ° C to obtain 18.6 g of a white crystal of the intermediate (B-12).

(2) Synthesis of intermediate (C-12):

Into a 100 mL three-necked flask equipped with a Dean-Stark trap, 17.7 g of an intermediate (B-12), 7.3 g of malononitrile, 4.6 mL of acetic acid, and 1.5 g of ammonium acetate were placed. Toluene (20 mL) was refluxed in an oil bath at 125 °C. After stirring for 1 hour, 4.6 mL of acetic acid and 1.5 g of ammonium acetate were additionally added, and the mixture was stirred under reflux for 2 hours. After standing to cool, 30 mL of methanol was added and stirred in an ice bath for 30 minutes. After crystallization was collected by filtration, it was washed with 20 mL of cold methanol and then dried. 12.1 g of white crystals of Intermediate (C-12) were obtained.

(3) Synthesis of intermediate (D-12)

To a solution of 11.3 g of an intermediate (C-12) and 20 mL of ethanol, 1.5 g of sulfur was added, followed by dropwise addition of 6.6 mL of triethylamine. After stirring at an internal temperature of 50 ° C for 30 minutes, 500 mL of ethyl acetate and 300 mL of water were added, and after shaking, liquid separation was carried out. 200 mL of brine was added to the organic layer, and after shaking, liquid separation was performed, and then magnesium sulfate was added to the organic layer and dried. After distilling off the organic solvent, 50 mL of isopropyl alcohol was added, and the mixture was suspended and suspended, and the crystals were collected by filtration. After drying at 80 ° C, 8.1 g of a white crystal of Intermediate (D-12) was obtained.

(4) Synthesis of intermediate (F-12)

6.0 g of the intermediate (E-11) was added to 60 mL of water and stirred at room temperature, and 5.6 mL of 12N hydrochloric acid was added dropwise thereto, followed by cooling to an internal temperature of 4 °C. At the internal temperature 4 mL of an aqueous solution of 1.3 g of sodium nitrite was added dropwise at 5 ° C or lower. After stirring at an internal temperature of 5 ° C or lower for 2 hours, 0.1 g of urea was added, followed by stirring for 15 minutes to obtain a diazo solution.

Further, 3.4 g of the intermediate (D-12) and 12.0 g of lithium acetate were dissolved in 90 mL of methanol and 10 mL of dimethylacetamide at room temperature, and the internal temperature was cooled to 4 ° C, and then the internal temperature was 5 The previous diazonium solution was added dropwise over 15 minutes at °C. After the internal temperature was stirred at 4 ° C or lower for 1.5 hours, 20.0 g of lithium chloride was added, and then 75 mL of acetonitrile was added dropwise. After crystallization was collected by filtration, it was washed with acetonitrile. The isolated crystals were suspended by using 75 mL of isopropyl alcohol at an internal temperature of 50 °C. The crystals were collected by filtration and washed with isopropyl alcohol. After drying at 80 ° C, 6.4 g of a brown crystal of the intermediate (F-12) was obtained.

(5) Synthesis of BLACK-31

The solution of 5.0 g of intermediate (F-12) and 3.7 g of intermediate (G) and 50 mL of water was adjusted to pH 2 or less with 12N hydrochloric acid water, and isoamyl nitrite was added dropwise at an internal temperature of 35 ° C to 40 ° C. Ester 1.2 g. After stirring at an internal temperature of 40 ° C for 3 hours, 50.0 g of lithium chloride was added and the internal temperature was cooled to 25 ° C. After crystallization was collected by filtration, it was washed with 150 mL of isopropyl alcohol. The isolated crystals were added to 200 mL of methanol, and the internal temperature was raised to 40 ° C, and then 800 mL of acetonitrile was added dropwise. After the dropwise addition, the mixture was stirred for 15 minutes, and then the internal temperature was cooled to 25 °C. After crystallization was collected by filtration, it was added to 150 mL of water, and then 450 mL of isopropyl alcohol was added dropwise at room temperature. After crystallization was collected by filtration, it was added to 50 mL of water, and then a 4 M aqueous lithium hydroxide solution was added until the pH became 8.3. To the solution, 150 mL of isopropyl alcohol was added dropwise, and the precipitated crystals were collected by filtration. After washing with 50 mL of isopropyl alcohol, it was dried at 80 ° C to obtain (BLACK-31) (M: Li). Black crystals 4.3g.

Next, the synthesis method of the phthalocyanine-based dye derivative of the present invention will be described in detail, but the starting material, the dye intermediate, and the synthesis route are not limited.

The phthalocyanine compound of the present invention can be derived, for example, according to the following synthetic route. In the following examples, λmax is the maximum absorption wavelength, and εmax is the molar absorption coefficient at the maximum absorption wavelength.

[Synthesis Example 4]

(1) Synthesis of Compound (A)

26.0 g of 4-nitrophthalonitrile (Tokyo Chemicals Co., Ltd.) was dissolved in 200 mL of Dimethyl sulfoxide (DMSO) under a nitrogen gas stream, and stirred at an internal temperature of 20 ° C. 30.3 g of sodium 3-mercapto-propane-sulfonate (Aldrich) was added. Then, 24.4 g of anhydrous sodium carbonate was slowly added during the stirring at an internal temperature of 20 °C. While stirring the reaction solution, the temperature was raised to 30 ° C and stirred at the same temperature for 1 hour. After cooling to 20 ° C, the reaction solution was filtered with a suction filter, and the filtrate was poured into 15000 mL of ethyl acetate to carry out crystallization, followed by stirring at room temperature for 30 minutes, and the precipitated crude crystals were separated by a suction filter. It was filtered, washed with ethyl acetate, and dried. The obtained crude crystals were recrystallized from methanol / ethyl acetate to give 42.5 g of Compound A. ¹ H-NMR (DMSO-d6), δ value TMS benchmark: 1.9~2.0 (2H, t); 2.5~2.6 (2H, m); 3.2~3.3 (2H, t); 7.75~7.85 (1H, d) ;7.93~8.03(1H,d);8.05~8.13(1H,s)

(2) Synthesis of Compound (B)

42.0 g of the compound (A) was dissolved in 300 mL of acetic acid, and during the stirring at an internal temperature of 20 ° C, 2.5 g of Na ₂ WO _{4 was added} . 2H ₂ O, then cooled in an ice bath until the internal temperature was 10 °C. Then, 32 mL of hydrogen peroxide water (30%) was slowly added dropwise while paying attention to the fever. After stirring at an internal temperature of 15 ° C to 20 ° C for 30 minutes, the reaction solution was warmed to an internal temperature of 60 ° C, and stirred at the same temperature for 1 hour. After cooling to 20 ° C, 1500 mL of ethyl acetate was poured into the reaction liquid, followed by stirring at the same temperature for 30 minutes, and then the precipitated crude crystal was filtered by a suction filter, and then washed with 200 mL of ethyl acetate. And dry it. The obtained crude crystals were heated and washed with methanol/ethyl acetate, and then purified to obtain 40.0 g of Compound B. ¹ H-NMR (DMSO-d6), δ value TMS benchmark: 1.8~1.9 (2H, t); 2.4~2.5 (2H, m); 3.6~3.7 (2H, t); 8.3~8.4 (1H, d) ;8.4~8.5(1H,d);8.6~8.7(1H,s)

(3) Synthesis of exemplified compound 102β (dye 1A of the general formula (1))

70 mL of n-pentanol was added to a three-necked flask equipped with a cooling tube, and 6.7 g of a compound B and 1.0 g of copper (II) chloride were added thereto, and 7.0 mL of 1,8- was added dropwise at room temperature while stirring. Diazabicyclo[5.4.0]-7-undecene (DBU). Then, the reaction liquid was warmed to an internal temperature of 100 ° C, and stirred at the same temperature for 10 hours. After cooling to 40 ° C, 250 mL of warmed methanol at 50 ° C was poured and stirred under reflux for 1 hour. Then, after cooling the reaction liquid to room temperature, the obtained solid was filtered by a suction filter, and then washed with 200 mL of methanol. Then, the obtained solid was added to 100 mL of a 1 M aqueous hydrochloric acid solution saturated with sodium chloride to elute the unreacted copper salt. After filtering the insoluble matter, 300 mL of methanol was added dropwise to the filtrate to carry out crystallization, and the obtained crude crystals were filtered by a suction filter, and then washed with 200 mL of methanol. After the crude crystals were dissolved in 50 mL of water, 100 mL of a saturated methanol solution of sodium acetate was slowly added while stirring the aqueous solution to carry out salt formation. Further, while stirring, the temperature was raised to the reflux temperature, and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, the precipitated crystals were filtered and washed with methanol. Then, the obtained crystal was added to 100 mL of methanol (100 mL), and the mixture was stirred under reflux for 1 hour, and after cooling to room temperature, the precipitated crystal was filtered, and the obtained crystal was added to 100 mL of a 70% methanol aqueous solution. After crystallizing, the mixture was refluxed for 1 hour, and after cooling to room temperature, the precipitated crystal was filtered, washed with 100 mL of methanol, and dried to obtain 3.8 g of the exemplified compound 102β as a blue crystal.

Λmax (maximum absorption wavelength): 629.1 nm; εmax (mole absorption coefficient at the maximum absorption wavelength) = 6.19 × 10 ⁴ (in an aqueous solution). The obtained compound was analyzed (measured by various analytical methods such as mass spectrometry: Electrospray Ionization-Mass Spectrometry (ESI-MS), elemental analysis, and neutralization titration), and the results were confirmed. The copper(II)-substituted position of the phthalocyanine as defined in the specification is a β-position substitution type {(2 or 3 position), (6 or 7 position), (10 or 11 position) of each benzene nucleus, (14 or 15) has 1 -{SO ₂ -(CH ₂ ) ₃ -SO ₃ Na} group, and has a total of 4 -{SO ₂ -(CH ₂ ) ₃ in one molecule of copper phthalocyanine -SO ₃ Na} base}.

(Synthesis Example 5)

The dye represented by the formula (YELLOW-1) (described as the formula (Y-1) in the following scheme) of the present invention can be derived, for example, according to the following synthesis route.

In the following examples, λmax is the maximum absorption wavelength, and εmax is the molar absorption coefficient at the maximum absorption wavelength.

Add compound (a) (2-amino-5-mercapto-1,3) to 450 mL of DMF (N,N-dimethylformamide) and 24.75 g of 1,2-dichloroethane at room temperature. , 4-thiadiazole (Wako Pure Chemical Industries, Ltd. / Catalog No. 019-11125)) 76.5g, After adding 79.5 g of potassium carbonate, the temperature was raised to 70 ° C, and stirred at the same temperature for 30 minutes. Then, 375 mL of warm water of 80 ° C was dropwise added to the above reaction liquid over 10 minutes, and then the internal temperature was cooled to 25 ° C. The precipitated crystals were collected by filtration, washed with 250 mL of ion-exchanged water, followed by washing with 150 mL of methanol, and then dried at 70 ° C overnight to obtain 65.1 g of compound (b).

After aminoisophthalic acid ((Wako Pure Chemical Industries, Ltd. manufacturing / catalog number 322-26175)) (A) 181.2g was suspended in 1000ml of ion-exchanged water, 257mL of concentrated hydrochloric acid was added, and it was ice bath Keep it at 5 °C. 116 ml of an aqueous solution of 69.7 g of sodium nitrite (reaction liquid A) was added dropwise thereto. 1300 ml of an aqueous solution of 378.1 g of sodium sulfite was stirred at an internal temperature of 25 ° C, and then the above reaction liquid A was poured thereinto. After stirring for 30 minutes in this state, the internal temperature was heated to 30 ° C, and then stirred for 60 minutes. 500 mL of hydrochloric acid was added to the reaction liquid, and the internal temperature was immediately raised to 50 ° C (reaction liquid B). After stirring for 90 minutes in this state, 125.2 g of trimethylacetamidoacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd. / catalog number P1112) and 100 mL of isopropyl alcohol were added to the above reaction liquid B, and the internal temperature was raised. Until 93 ° C, then stir for 240 minutes. After cooling to room temperature, the precipitated crystals (C) were suction-filtered, and the crystals were washed with 1500 mL of ion-exchanged water, and then the crystals were washed with 1000 mL of isopropyl alcohol, followed by drying. The isolated yield was 223.5 g. The yield was 73.7%.

To a solution of 100 mL of methanesulfonic acid, 120 mL of acetic acid, and 180 mL of propionic acid, 29.2 g of the compound (b) was added, and the internal temperature was raised to 45 ° C to obtain a homogeneous solution, and then the internal temperature was cooled to 0 ° C. Then, while maintaining the internal temperature at 0 ° C to 10 ° C, a solution of 14.7 g of NaNO ₂ and 27 mL of ion-exchanged water was added dropwise to the above homogeneous solution, and the mixture was stirred at an internal temperature of 5 ° C for 15 minutes to prepare a diazo. salt. The diazonium salt was added dropwise to a solution prepared by previously preparing the coupling agent component (C) 60.6 g, methanol 600 mL, and ethylene glycol 600 mL prepared at a temperature of 0 ° C to 10 ° C in the internal temperature. Solution. Then, the mixture was stirred at an internal temperature of 25 ° C for 30 minutes. The precipitated crystals were filtered, washed with 250 mL of methanol, and then the crude crystals were dispersed in 650 mL of water, and then stirred at an internal temperature of 80 ° C for 30 minutes, then cooled to room temperature, and then filtered, using water. After washing with 300 mL, it was dried overnight at 60 ° C to obtain 64.47 g of a pigment (D).

46.1 g of the dye (D) prepared in the above Synthesis Example 3 was added to and dissolved in a solution of 16.5 g of KOH (tablet) and 414.9 mL of ion-exchanged water prepared in advance at an internal temperature of 20 ° C to 30 ° C. .

Then, a solution of 40.0 g of potassium acetate and 200 mL of methanol was added dropwise to the above aqueous dye solution at an internal temperature of 25 ° C, followed by stirring at the same temperature for 10 minutes. Thereafter, 2488 mL of IPA (isopropyl alcohol) was added dropwise to carry out salt formation, and the mixture was stirred at the same temperature for 30 minutes, and then filtered, and then washed with IPA 500 mL, and dried at 70 ° C overnight to obtain 44 g of a pigment (YELLOW-1). The crude crystals.

After dissolving 8.7 g of crude crystals (YELLOW-1) in 78.3 mL of ion-exchanged water at room temperature, the pH of the aqueous solution was adjusted to 8.5 using 0.1 N hydrochloric acid, and filtered through a 0.2 μm membrane filter. IPA 391.5 mL was added dropwise to the filtrate at an internal temperature of 25 °C. The precipitated crystals were filtered, washed with 100 mL of IPA, and dried overnight at 80 ° C to obtain fine crystals of 7.8 g of a pigment (YELLOW-1). {λmax: 428 nm (H ₂ O), ε max: 4.20 × 10 ⁴ } With respect to (YELLOW-2) and (YELLOW-3), it can also be synthesized by the same method as (YELLOW-1).

[Preparation of each ink composition]

The cyan ink composition was added to deionized water and added to 100 g of the phthalocyanine dye shown in the following Table 5 and the other components shown below, and the mixture was stirred while heating at 30 to 40 ° C for 1 hour. Thereafter, PH = 9 was prepared by using NaOH 10 mol/L, and then filtered under reduced pressure using a microfilter having an average pore diameter of 0.25 μm to prepare a cyan ink liquid.

Phthalocyanine dye (dye of formula (1))

Phthalocyanine dye (dye of formula (2))

With respect to the yellow ink composition, the magenta ink composition, and the black ink composition, the components were stirred at room temperature for 30 minutes according to the compositions shown in Tables 1, 2, and 4 below, and then the pore diameter was 1.0 μm. Membrane filter pair obtained The solution was filtered to thereby obtain each ink composition. In Tables 1, 2, and 4, the numerical value of each component indicates the mass % of each component when the mass of the ink composition is 100%, and the "residual" indicating the amount of water indicates water. The other components are added together in an amount of 100%.

The details of the compounds used in the respective ink compositions are shown below.

‧TEGmBE: triethylene glycol monobutyl ether

‧DEGmBE: Diethylene glycol monobutyl ether

‧Acetylenol E100: acetylene glycol surfactant, manufactured by Kawaken Fine Chemicals

‧Olfine E1010: acetylene glycol surfactant, manufactured by Nissin Chemical Co., Ltd.

‧Olfine PD001: acetylene glycol surfactant, manufactured by Nissin Chemical Co., Ltd.

‧Surfynol 104PG50: acetylene glycol surfactant, manufactured by Gas Products and Chemicals

‧PROXEL XL2: 1,2-Dibenzoisothiazolin-3-one, manufactured by Arch

‧YELLOW-R1: C.I. Direct Yellow 132

‧YELLOW-R2: C.I. Direct Yellow 86

‧C.I. Acid Red 289: Made by Tokyo Chemical Industry Co., Ltd.

‧C.I. Acid Blue 9: Made by Tokyo Chemical Industry Co., Ltd.

Comparative compound 3 (ratio of substitution position α/β=50/50)

The ink compositions having the compositions shown in Tables 1, 2, and 4 were used, and Examples 1 to 15 and Comparative Examples 1 to 7 were produced according to the combination of the ink compositions shown in Table 5 below. Ink set.

With respect to the ink set shown in Table 5, the ink storage stability of each ink composition in the ink set was evaluated as follows.

In addition, using an inkjet printer Stylus Color 880 (trademark) (trade name, Seiko Epson Co., Ltd.), and further using the ink set shown in Table 5, it will contain yellow (Y), magenta (M), cyan (Cy), and black (Bk), and the concentration varies with the optical density (OD) of each color. A monochrome image pattern of various colors varying in a stepwise manner from 0.7 to 1.8, and an image pattern of green, red, and gray printed on an inkjet recording medium {photo paper <gloss> (trade name, Seiko Epson Co., Ltd.) Made)}.

[Ink storage stability]

The ink composition was stored in a closed container, and the storage stability during one month was confirmed at room temperature (18 to 20 ° C). The pigment content (dye content) in the ink before and after storage was measured by high performance liquid chromatography (LC20 manufactured by Shimadzu Corporation) and evaluated as a residual ratio of the dye. The residual ratio of the pigment was 90% or more, and the residual ratio of the dye was 80% or more, and the remaining content of 90% was B. The residual ratio of the dye was less than 80%, and C was evaluated in three stages. The higher the residual ratio of the pigment, the more excellent the ink storage stability. The evaluation results are shown in Tables 6 and 7.

[light resistance]

The glossy paper on which the image was formed was irradiated with a calender (100,000 lux) for 28 days, and the image density before and after the krypton irradiation was measured using a reflection densitometer (X-Rite 310TR), and the OD of each color monochrome image was measured. value. Further, the above reflection density was measured at three points of 0.7, 1.0, and 1.8. Based on the obtained results, the optical density residual ratio (ROD) was obtained by the following formula: ROD (%) = (D/D ₀ ) × 100 (wherein D represents the OD value after light irradiation, and D ₀ represents light irradiation. The previous OD value).

When the ROD is 85% or more at any concentration, it is set to A, and when the ROD of any one point is less than 85%, it is B, and the ROD of any two points is less than 85% of C. The case where all concentrations of ROD were less than 85% was set to D, and evaluation was performed in four stages.

Even if exposed to light for a long period of time, the decrease in ROD is less, and the light resistance is superior. The evaluation results are shown in Tables 6 and 7.

In addition, based on the results of the light resistance evaluation of each color, the light resistance of each ink set was classified by the following criteria. The evaluation results obtained are shown in Table 7 as "light resistance" of the ink set.

A: The light resistance evaluation is that all four colors are A.

B: Light resistance evaluation is one of four colors, B or more, and the remaining colors are A.

C: Light resistance evaluation is one of the four colors, C or more, and the remaining colors are A or B.

D: Light resistance evaluation is one of four colors and D is D or more.

Further, the ink set is evaluated for the difference (color balance) of the ROD change between the respective colors of the printed matter caused by exposure to light.

A: Even after 28 days from the start of light irradiation, the difference between the maximum value and the minimum value in the ROD of each color (hereinafter, referred to as "the difference in ROD" in the description of the evaluation method) is less than 15 points (15%). ).

B: The ROD difference becomes 15 points from 15 days to 28 days from the start of the light irradiation.

C: The difference in ROD becomes 15 points within 8 to 14 days from the start of light irradiation.

D: Within 7 days from the start of the light irradiation, the difference in ROD becomes 15 points.

The difference in ROD in this evaluation was excellent as a recorded matter. The evaluation results obtained are shown in Table 7 as "color balance 1".

[Ozone resistance]

The glossy paper on which the image was formed was placed for 14 days under the conditions of setting the ozone gas concentration to 5 pm (25 ° C, 60% RH), and the image before and after the ozone gas was measured using a reflection densitometer (X-Rite 310TR). The concentration, and the OD value of each color monochrome image was measured. Further, the above reflection density was measured at three points of 0.7, 1.0, and 1.8. Based on the obtained results, the optical density residual ratio (ROD) was determined by the following formula: ROD (%) = (D / D ₀ ) × 100 (wherein D represents the OD value after standing under ozone gas, D ₀ Indicates the OD value before placement under ozone gas).

When the ROD is 85% or more at any concentration, it is set to A, and when the ROD of any one point is less than 85%, it is B, and the ROD of any two points is less than 85% of C. The case where all concentrations of ROD were less than 85% was set to D, and evaluation was performed in four stages.

Even if exposed to ozone gas for a long time, the decrease in ROD is less, and the ozone resistance is superior. The evaluation results are shown in Table 6.

In addition, based on the results of the evaluation of the ozone resistance of each color, the classification of ozone resistance as the respective ink sets was performed using the following criteria. The evaluation results obtained are shown in Table 7 as "the ozone resistance of the ink set".

A: Evaluation of ozone resistance is that all four colors are A.

B: Evaluation of ozone resistance is one of the four colors, B or more, and the remaining colors are A.

C: Evaluation of ozone resistance is one of the four colors, C or more, and the remaining colors are A or B.

D: Evaluation of ozone resistance is one of four colors, and D is D or more.

Further, the difference (color balance) of the ROD change between the respective colors of the printed matter caused by exposure to ozone was evaluated for each ink set using the following criteria.

AA: Even after 21 days from the start of ozone gas, the difference between the maximum value and the minimum value in the ROD of each color (hereinafter, referred to as "the difference in ROD" in the description of the evaluation method) is less than 15 points ( 15%).

A: The ROD difference becomes 15 points within 15 to 21 days from the start of the ozone gas.

B: The ROD difference becomes 15 points within 8 to 14 days from the start of the ozone gas.

C: The difference in ROD becomes 15 points within 4 to 7 days from the start of the placement under ozone gas.

D: Within 3 days from the start of the ozone gas, the difference in ROD becomes 15 points.

The difference in ROD in this evaluation was excellent as a recorded matter. The evaluation results obtained are shown in Table 7 as "color balance 2".

[Image density]

In addition, an inkjet printer Stylus Color 880 (trademark) (trade name, manufactured by Seiko Epson Co., Ltd.) was used, and the ink set shown in Table 5 was used, and it was made on plain paper (Canon, GF-500). (Product name)) is printed on, and then the maximum image density is measured using a reflection densitometer (X-rite310TR), and The image density of each single color was measured, and the evaluation was performed by the following evaluation criteria.

A: The image density is 1.1 or more in all colors.

B: One of the four colors is 1.0 or more and less than 1.1, and the remaining colors are A.

C: One of the four colors is less than 1.0 or more, and the remaining colors are A or B.

The obtained evaluation results are shown in Table 7 as image density.

According to the above results, it is understood that the ink set of the present invention is excellent in ink storage stability, and can obtain an image excellent in print density, good color balance, and excellent fading balance due to excellent ozone gas fastness and light fastness (recording) ()).

[Industrial availability]

Since the ink set of the present invention uses a specific compound as a coloring agent for the cyan ink composition, the ink storage stability is excellent. The image obtained by using the ink set has a high print density, good color balance, and excellent fading balance. Excellent in oxygen gas firmness and light fastness.

While the invention has been described in detail with reference to the specific embodiments the embodiments

The present application is based on Japanese Patent Application No. 2012-251705, filed on Jan.

Claims (22)

An ink set comprising at least a black ink composition, a yellow ink composition, a magenta ink composition, and a cyan ink composition, wherein the black ink composition is selected from the group consisting of the following formula (B-1) At least one of the group consisting of a compound containing a phthalocyanine dye represented by the following formula (1) and a group represented by the following formula (2) Phthalocyanine dye as a coloring agent, (In the formula (B-1), A represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted nitrogen-containing 5-membered heterocyclic group; G represents a nitrogen atom or -C(R ₂ )= R ₂ represents a hydrogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted amine carbenyl group, or a cyano group; and Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent; Y ₂ , Y ₃ and Y ₄ may be bonded to each other to form a ring; Y ₂ , Y ₃ and Y ₄ do not simultaneously represent a hydrogen atom; M independently represents a hydrogen atom or a monovalent counter cation) In the formula (1), R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime a group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group; Further having a substituent; Z ₁ , Z ₂ , Z ₃ , and Z ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic; wherein Z ₁ , Z ₂ , Z ₃ , and Z ₄ having at least one ionic Aqueous group as a substituent; l, m, n, p , q 1, q 2, q 3 and q ₄ each independently represent 1 or 2; M ₁ represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide Or a metal halide; In the formula (2), R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ and R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Aralkyl, aryl, heterocyclic, cyano, hydroxy, nitro, amine, alkylamino, alkoxy, aryloxy, decylamino, arylamino, ureido, aminoxime Amino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino group, amine carbaryl group, amine sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, oxime a group, an amine methyl methoxy group, a decyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, a quinone imine group, a heterocyclic thio group, a phosphonium group, a fluorenyl group or an ionic hydrophilic group; Further having a substituent; Z ₅ , Z ₆ , Z ₇ , and Z ₈ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted Alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heterocyclic; wherein Z ₅ , Z ₆ , Z ₇ , and Z ₈ having at least one ionic Aqueous group as a substituent; t, u, v, w , q 5, q 6, q 7 and q ₈ each independently represent 1 or _2; M 2 represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide Or metal halides. The ink set according to claim 1, wherein the black ink composition further contains a compound represented by the following formula (B-14), In the formula (B-14), the A ring, the B ring and the C ring each independently represent a substituted or unsubstituted aryl or 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 And C ₁ , C ₂ , C ₃ , C ₄ , C ₁₁ , C ₁₂ , C ₁₃ , and C ₁₄ each independently represent a hydrogen atom or a substituent; and Q ₁ and Q ₂ each independently represent a hydrogen atom or a substituent; ₁₂ represents a divalent linking group; wherein the compound of the formula (B-14) has at least one ionic hydrophilic group. The ink set according to claim 1, wherein the content of the coloring agent in the black ink composition is 0.1% by mass to 30% by mass based on the total mass of the black ink composition. The ink set according to claim 1, wherein R ₂ , R ₃ , R ₆ , R ₇ , R ₁₀ , R ₁₁ , R ₁₄ in the phthalocyanine dye represented by the general formula (1) R ₁₅ is a hydrogen atom. The ink set according to claim 1, wherein R ₁ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₂ , R ₁₃ in the phthalocyanine dye represented by the general formula (2) R ₁₆ is a hydrogen atom. The ink set according to claim 1, wherein Z ₁ , Z ₂ , Z ₃ , and Z ₄ in the phthalocyanine dye represented by the general formula (1) independently represent substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The ink set according to claim 1, wherein Z ₅ , Z ₆ , Z ₇ , and Z ₈ in the phthalocyanine dye represented by the general formula (2) independently represent substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The ink set according to claim 1, wherein Z ₅ , Z ₆ , Z ₇ , and Z ₈ in the phthalocyanine dye represented by the general formula (2) represent a substituted alkyl group, and the alkyl group At least one of the substituents has a -SONHR group (wherein R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group). The ink set according to claim 1, wherein l, m, n and p in the phthalocyanine dye represented by the general formula (1) are 1. The ink set according to claim 1, wherein t, u, v, and w in the phthalocyanine dye represented by the general formula (2) are 1. The ink set according to claim 1, wherein q ₁ , q ₂ , q ₃ and q ₄ in the phthalocyanine dye represented by the general formula (1) are 2. The ink set according to claim 1, wherein q ₅ , q ₆ , q ₇ and q ₈ in the phthalocyanine dye represented by the general formula (2) are 2. The ink set according to claim 1, wherein the mass ratio of the phthalocyanine dye represented by the general formula (1) to the phthalocyanine dye represented by the general formula (2) is 50/50 to 10/ 90. The ink set according to any one of the items 1 to 13, wherein the content of the phthalocyanine dye represented by the formula (1) in the cyan ink composition is 0.1% by mass to 10%. quality%. The ink set according to any one of claims 1 to 13, which comprises a compound selected from the group consisting of a compound represented by the following formula (Y) and a formula (Y-2) a yellow ink composition as a colorant of at least one compound represented by the compound and a salt thereof; wherein the general formula (Y-2) does not contain the general formula (Y); the general formula (Y): (In the general formula (Y), M each independently represents a hydrogen atom or a cation, and when M represents a cation, it means a Li ⁺ ion, a Na ⁺ ion, a K ⁺ ion or an NH ₄ ⁺ ion); In the formula (Y-2), R ₄ represents a monovalent group, R ₅ represents -OR ₆ or -NHR ₇ , R ₆ and R ₇ represent a hydrogen atom or a monovalent group, and X ₃ represents a divalent linking group. , n ₃ is 0 or 1, Ar ₃ represents a divalent heterocyclic group, and Ar ₄ represents an alkyl group, an aryl group or a monovalent triazine ring group. An ink set as described in claim 15 wherein the ink set is opposite to the upper The total mass of the yellow ink composition is from 1.0% by mass to 6.0% by mass based on the total amount of the coloring agent in the yellow ink composition. The ink set according to any one of claims 1 to 13, which comprises a group selected from the group consisting of a compound represented by the following formula (M-1) and a salt thereof. At least one magenta ink composition as a colorant, In the formula (M-1), A _M represents a 5-membered heterocyclic group; B ₁ and B ₂ respectively represent -CR ₁₃ =, -CR ₁₄ =, or B ₁ and B ₂ each represent a nitrogen atom; The other represents -CR ₁₃ = or -CR ₁₄ =; R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group, a mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonyl group; each group may further have a substituent; wherein R ₁₁ , R _{12 is} not a hydrogen atom at the same time; G, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an arylalkyl group, an aryl group, a heterocyclic group, a cyano group or a carboxyl group. Aminomethyl, alkoxycarbonyl, aryloxycarbonyl, decyl, hydroxy, alkoxy, aryloxy, nonyloxy, decyloxy, aminemethyloxy, heterocyclic oxy, alkoxy A carbonyloxy group, an aryloxycarbonyloxy group, an amine group substituted with an alkyl group or an aryl group or a heterocyclic group, a mercaptoamine group, a urea group, an aminesulfonylamino group, an alkoxycarbonylamino group, an aryloxy group Carbocarbonylamine, alkylsulfonylamino or arylsulfonyl Base, nitro, alkylthio, arylthio, alkylsulfonyl or arylsulfonyl, alkylsulfinyl or arylsulfinyl, aminesulfonyl, heterocyclicthio, or An ionic hydrophilic group; each group may be further substituted; in addition, R ₁₃ and R ₁₁ or R ₁₁ and R ₁₂ may be bonded to form a 5-membered ring or a 6-membered ring; wherein the formula (M-1) has At least one ionic hydrophilic group. An ink cartridge that accommodates the ink set as described in any one of claims 1 to 13. An ink jet printer loaded with an ink cartridge as described in claim 18 of the patent application. An ink jet recording method characterized in that recording is performed using the ink set as described in any one of claims 1 to 13. An ink jet recording method, characterized in that an image is formed using the ink set as described in any one of claims 1 to 13. A recorded matter characterized by being recorded using an ink set as described in any one of claims 1 to 13.