JP2019081852A - Inkjet ink composition - Google Patents

Abstract

To provide an inkjet ink composition that is suppressed in the occurrence of clogging in a discharge nozzle or the like as compared with the conventional one by enhancing color reproducibility and in addition, enhancing color developability.SOLUTION: The inkjet ink composition includes: a magenta dye of a special structure; and one or more kinds of either of a yellow dye and a cyan dye in which the basic skeleton of the dye has a symmetric structure and the dye has a maximum absorption wavelength in the range other than the range of 500 to 560 nm.SELECTED DRAWING: None

Description

  The present invention relates to inkjet ink compositions.

  The ink jet recording method is a printing method in which droplets of ink are discharged from a discharge nozzle of an ink jet recording apparatus and adhered to a recording medium such as paper to produce a printed matter. Conventionally, in addition to inks of basic colors of cyan, magenta, yellow and black, so-called secondary color inks such as red, green and blue for securing color reproducibility have been known.

  For example, in the ink set described in Patent Document 1, improvement of color reproducibility by adding a red ink as a secondary color ink has been proposed.

Japanese Patent Application No. 2013-224603

  However, in the red ink described in Patent Document 1, a magenta dye having an anthrapyridine skeleton is used as a coloring material. In general, magenta dyes having an anthrapyridine skeleton may have low color developability. Therefore, it is necessary to increase the content (solid content concentration) of the dye in the ink composition in order to ensure the color forming property, and the clogging by the drying of the dye or the like in the discharge nozzle tends to be aggravated. was there.

  Therefore, it is an object of the present invention to improve the color reproducibility as well as to improve the color developability, thereby suppressing the occurrence of clogging in the discharge nozzle and the like as compared with the conventional ink composition. An ink composition is provided.

  The present invention has been made to solve at least a part of the above-described problems, and can be realized as the following modes or application examples.

  Application Example 1 In the ink jet ink composition according to this application example, the magenta dye represented by the following general formula (1-1) and the basic dye skeleton have a symmetrical structure, and the maximum absorption wavelength is from 500 nm to 560 nm And one or more kinds of yellow dyes and cyan dyes.

（一般式（１−１）において、Ｒ¹、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、およびＲ²⁰は、それぞれ独立に水素原子または置換基であり、Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のヘテロ環基、置換もしくは無置換のアルキルスルホニル基、置換もしくは無置換のアリールスルホニル基、置換もしくは無置換のアルコキシカルボニル基、置換もしくは無置換のアリールオキシカルボニル基、カルバモイル基、置換もしくは無置換のモノアルキルアミノカルボニル基、置換もしくは無置換のジアルキルアミノカルボニル基、置換もしくは無置換のモノアリールアミノカルボニル基、置換もしくは無置換のジアリールアミノカルボニル基、または置換もしくは無置換のアルキルアリールアミノカルボニル基である。）

(In the general formula (1-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and R ¹⁰¹ and R ¹⁰² each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted Aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl Group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group Substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.)

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using the magenta dye represented by the general formula (1-1). It was completed. That is, by containing the above-mentioned magenta dye and at least one of yellow dye and cyan dye having a dye basic skeleton having a symmetrical structure and having a maximum absorption wavelength other than the range of 500 nm to 560 nm, It is possible to provide a secondary color inkjet ink composition in which the color reproducibility and color development of the printed matter are further improved and clogging in the discharge nozzle is less likely to occur.

  Application Example 2 In the inkjet ink composition described in the application example, the content of the magenta dye represented by the general formula (1-1) is 0.1 mass to the total mass of the inkjet ink composition. It is preferable that it is the range of% or more and 2.4 mass% or less.

  According to this, since the color forming property of the magenta dye represented by the general formula (1-1) is high, the color forming property can be secured at a content lower than that of the prior art, and the above content is 0.1% by mass or more Thus, the color development can be improved. When the content is 2.4% by mass or less, the color developing property can be further improved, and furthermore, an ink composition in which clogging does not easily occur can be provided.

  Application Example 3 The inkjet ink composition described in the application example contains, as a yellow dye, at least one of yellow dyes represented by General Formula (2-1) and General Formula (2-2). Is preferred.

（一般式（２−１）において、Ｒ_Y1、Ｒ_Y2、Ｙ₁、およびＹ₂は、１価の基であり、Ｘ₁、Ｘ₂は、それぞれ独立にハメットのδｐ値０．２０以上の電子吸引性基である。Ｚ₁、Ｚ₂はそれぞれ独立に、水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアラルキル基、置換または無置換のアリール基、置換または無置換のヘテロ環基である。Ｍは、水素原子またはカチオンである。）

(In the general formula (2-1), R _Y1 , R _Y2 , Y ₁ and Y ₂ are monovalent groups, and X ₁ and X ₂ each independently have a Hammett δp value of 0.20 or more. Z ₁ and Z ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl Group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, and M is a hydrogen atom or a cation)

（一般式（２−２）において、Ｑはハロゲン原子である。Ｍは、水素原子、アルカリ金属、ＮＨ₄である。ｘ１は２以上、４以下の整数であり、ｙ１は１以上、３以下の整数である。）

(In the general formula (2-2), Q is a halogen atom. M is a hydrogen atom, an alkali metal, or NH _4. x1 is an integer of 2 or more and 4 or less, and y1 is 1 or more and 3 or less. Is an integer of

  According to this, since the yellow dye has a symmetrical structure, the association can be improved by mixing it with the magenta dye represented by the general formula (1-1). Therefore, the ink composition having high ozone resistance can be provided. In addition, the color gamut of the yellow region can be expanded to improve color reproducibility.

  Application Example 4 In the inkjet ink composition described in the application example, the mass ratio of the magenta dye represented by the general formula (1-1) to the yellow dye is 1.25 or more when the yellow dye is 1. And 3.00 or less.

  According to this, the color reproducibility can be improved by setting the mass of the yellow dye to not less than 1.25 times the mass of the magenta dye represented by the general formula (1-1). When the mass of the yellow dye is 3.00 or less times the mass of the magenta dye represented by the general formula (1-1), color reproducibility can be further improved, and clogging is further caused. It is possible to provide a difficult inkjet ink composition.

  Application Example 5 The ink-jet ink composition described in the application example may contain, as a cyan dye, at least one of cyan dyes represented by the following general formula (3-1) and the following general formula (3-2) Is preferred.

（一般式（３−２）において、破線で表される環Ａ₁，Ａ₂，Ａ₃，Ａ₄は、それぞれ独立にポルフィラジン環に縮環したベンゼン環または６員環の含窒素複素芳香環であり、含窒素複素芳香環の個数は、平均値で０．００を超えて３．００以下であり、残りはベンゼン環である。Ｒ₁は、炭素数が２以上、１２以下のアルキレン基である。Ｘは、置換基として、スルホ基、カルボキシ基、リン酸基、スルファモイル基、カルバモイル基、ヒドロキシ基、炭素数が１以上、６以下のアルコキシ基、アミノ基、炭素数が１以上、４以下の、モノアルキルアミノ基またはジアルキルアミノ基、炭素数が６以上、１０以下の、モノアリールアミノ基またはジアリールアミノ基、炭素数が１以上、３以下のアルキルカルボニルアミノ基、ウレイド基、炭素数が１以上、６以下のアルキル基、ニトロ基、シアノ基、ハロゲン原子、炭素数が１以上、６以下の、アルキルスルホニル基またはアルキルチオ基よりなる群から選択される１種類または２種類以上の置換基を有してもよい、スルホアニリノ基、カルボキシアニリノ基、ホスホノアニリノ基、スルホナフチルアミノ基、カルボキシナフチルアミノ基またはホスホノナフチルアミノ基である。Ｒは、水素原子、スルホ基、カルボキシ基、リン酸基、スルファモイル基、カルバモイル基、ヒドロキシ基、炭素数が１以上、６以下のアルコキシ基、アミノ基、炭素数が１以上、６以下の、モノアルキルアミノ基またはジアルキルアミノ基、モノアリールアミノ基、ジアリールアミノ基、炭素数が１以上、３以下のアルキルカルボニルアミノ基、ウレイド基、炭素数が１以上、６以下のアルキル基、ニトロ基、シアノ基、ハロゲン原子、炭素数が１以上、６以下のアルキルスルホニル基、またはアルキルチオ基である。基Ｆは、フェニル基または６員含窒素複素芳香環基であり、ｘ２は、炭素数が１以上、６以下のアルキレン基であり、ｂは平均値で０．００以上、３．９０未満であり、ｃは平均値で０．１０以上、４．００未満であり、かつｂおよびｃの和は、平均値で１．００以上、４．００未満である。）

(In the general formula (3-2), the rings A ₁ , A ₂ , A ₃ and A ₄ represented by broken lines are each independently a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring fused to a porphyrazine ring The number of nitrogen-containing heteroaromatic rings is, on average, more than 0.00 and not more than 3.00, and the remainder is a benzene ring R ₁ is an alkylene having 2 or more and 12 or less carbon atoms X is a substituent such as a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an amino group, 1 or more carbon atoms A monoalkylamino group or dialkylamino group having 4 or less carbon atoms, a monoarylamino group or a diarylamino group having 6 to 10 carbon atoms, an alkylcarbonylamino group having 1 to 3 carbon atoms and 3 or less carbon atoms, a ureido group, Charcoal One or more selected from the group consisting of an alkyl group having a prime number of 1 or more and 6 or less, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group or an alkylthio group having 1 or more and 6 or less carbon atoms A sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group or a phosphononaphthylamino group which may have a substituent, R represents a hydrogen atom, a sulfo group, a carboxy group, Phosphoric acid group, sulfamoyl group, carbamoyl group, hydroxy group, alkoxy group having 1 to 6 carbon atoms, amino group, monoalkylamino group or dialkylamino group having 1 to 6 carbon atoms, monoarylamino Group, a diarylamino group, an alkylcarbonylamino group having 1 or more and 3 or less carbon atoms, Id group, an alkyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group having 1 to 6 carbon atoms, or an alkylthio group F is a phenyl group or 6-membered nitrogen-containing heteroaromatic ring group, x 2 is an alkylene group having 1 to 6 carbon atoms, b is an average of 0.00 to less than 3.90, and c is an average 0.10 or more and less than 4.00, and the sum of b and c is 1.00 or more and less than 4.00 on average)

  According to this, since the above-mentioned cyan dye has a symmetrical structure, association can be improved by mixing it with the magenta dye represented by the general formula (1-1). Therefore, the ozone resistance of the printed matter can be improved. In addition, the color gamut of the cyan region can be expanded to improve color reproducibility.

  Application Example 6 In the inkjet ink composition described in the application example, the mass ratio of the magenta dye represented by the general formula (1-1) to the cyan dye is 1.00 or more when the cyan dye is 1. And 1.50 or less.

  According to this, the color reproducibility can be improved by setting the mass of the cyan dye to be 1.00 times or more of the mass of the magenta dye represented by the general formula (1-1). When the mass of the cyan dye is 1.50 times or less the mass of the magenta dye represented by the general formula (1-1), color reproducibility can be further improved, and clogging is further caused. It is possible to provide a difficult inkjet ink composition.

FIG. 1 is a schematic perspective view showing an example of an inkjet recording apparatus.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below is an example of the present invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications implemented within the scope of the present invention.

[Ink jet ink composition]
The ink jet ink composition is discharged as droplets from a discharge nozzle of an ink jet recording apparatus, and is used to adhere to a recording medium such as paper to produce a printed matter. In the present embodiment, a water-based inkjet ink containing water as a main medium will be described as an example. The secondary color ink (hereinafter, also simply referred to as “ink”) as the ink jet ink composition according to the present embodiment contains water, an organic solvent, a surfactant, and the like in addition to the dye as the coloring material. Hereinafter, the components described above contained in the ink of the present embodiment will be described.

(dye)
Among the dyes contained in the ink composition of the present embodiment, the substituent in the magenta dye represented by General Formula (1-1) is defined as a substituent group, and a specific example will be described.

  As a substituent group, 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 silyloxy group, a heterocyclic oxy Group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or Arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryl Examples include oxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyl oxy group, phosphinyl amino group, silyl group, ionic hydrophilic group It can be mentioned. These substituents may be further substituted, and examples of the additional substituent can include a group selected from the above-mentioned substituent group.

  Examples of the ionic hydrophilic group include sulfo group, carboxyl group, thiocarboxyl group, sulfino group, phosphono group, dihydroxyphosphino group, quaternary ammonium group and the like. Particularly preferred is a sulfo group or a carboxyl group. The ionic hydrophilic group may contain a cation or an anion, and a state containing a cation or an anion is called a salt state. The carboxyl group, phosphono group and sulfo group may be in the form of a salt, and examples of the salt-forming counter cation include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic cation (Eg, tetramethyl ammonium ion, tetramethyl guanidinium ion, tetramethyl phosphonium), lithium salt, sodium salt, potassium salt, ammonium salt is preferable, and sodium salt or mixed salt containing sodium salt as a main component More preferably, the sodium salt is most preferred.

  In the present embodiment, when the compound is a salt, the salt is dissociated into ions in the aqueous ink.

  Next, the magenta dye represented by formula (1-1) will be described. In the ink, the magenta dye represented by the general formula (1-1) (hereinafter sometimes referred to as magenta dye (1-1)) and the dye basic skeleton have a symmetrical structure, and the maximum absorption wavelength is 500 nm And one or more of yellow dyes and cyan dyes other than the range up to 560 nm.

  The magenta dye (1-1) has an amino group having a specific substituent. The mechanism of action is unknown, but when the magenta dye (1-1) has such a structure, the chroma, color development, light fastness, ozone fastness, and moisture fastness of the printed matter are improved.

In the general formula (1-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent. R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And when R ²⁰ is a substituent, examples of the substituent include substituents selected from the above-mentioned substituent group.

In the general formula (1-1), R ¹ , R ⁵ , R ⁶ and R ¹⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted one from the viewpoint of availability of raw materials and ease of synthesis Or a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a carboxyl group, or a halogen atom, preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted group. It is a substituted aryl group or a substituted or unsubstituted alkoxy group, particularly preferably a substituted or unsubstituted alkyl group. As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is more preferable. Moreover, as a substituent in case each group has a substituent, the substituent chosen from said substituent group is mentioned.

In the general formula (1-1), R ⁴ and R ⁹ each independently represent a hydrogen atom or a substitution from the viewpoints of availability of raw materials and synthesis, light resistance of printed matter, ozone resistance, color development and saturation. Or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted acylamino group, substituted or unsubstituted group Unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureide group, sulfo group, carboxyl It is preferably a group or a halogen atom, more preferably a hydrogen atom , Substituted or unsubstituted acylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted It is an unsubstituted aryl ureido group or a sulfo group, particularly preferably a hydrogen atom or a sulfo group. Moreover, the substituent chosen from said substituent group is mentioned as a substituent in case each group has a substituent.

In the general formula (1-1), R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, from the viewpoint of availability of raw materials and easiness of synthesis. Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted acylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonyl It is preferably an amino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, a sulfo group, a carboxyl group, or a halogen atom, and more preferably hydrogen An atom, a substituted or unsubstituted alkyl group, or It is a ruho group, particularly preferably a substituted or unsubstituted alkyl group. As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is more preferable. Moreover, as a substituent in case each group has a substituent, the substituent chosen from said substituent group is mentioned.

In the general formula (1-1), R ¹¹ , R ¹⁴ , R ¹³ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently hydrogen from the viewpoint of availability of raw materials and easiness of synthesis It is preferably an atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a hydroxy group, a halogen atom, or a sulfo group, More preferably, it is a hydrogen atom, a hydroxy group, a halogen atom or a sulfo group, and particularly preferably a hydrogen atom. Moreover, as a substituent in case each group has a substituent, the substituent chosen from said substituent group is mentioned.

In the general formula (1-1), R ¹² and R ¹⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, from the viewpoint of availability of raw materials and easiness of synthesis. A halogen atom or a sulfo group is preferable, more preferably a hydrogen atom or a sulfo group. Moreover, as a substituent in case each group has a substituent, the substituent chosen from said substituent group is mentioned.

Further, from the viewpoint of solubility in water, in the general formula (1-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , At least one of R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ has an ionic hydrophilic group such as a carboxyl group, a sulfo group or a phosphono group preferable. Examples of counter cations of these ionic hydrophilic groups include hydrogen atoms (protons), alkali metal cations (lithium ions, sodium ions or potassium ions), ammonium ions and the like. Among these, alkali metal cations are preferable from the viewpoint of easiness of synthesis (easiness of handling as dye powder).

In formula (1-1), R ¹⁰¹ and R ¹⁰² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group Group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkyl It is an aminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group.

The alkyl group in the case where R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted alkyl groups is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. And methyl and ethyl are more preferred. When the alkyl group has a substituent, examples of the substituent include the substituents selected from the above-mentioned substituent group, and an aryl group is preferable, and a phenyl group is particularly preferable.

The aryl group in the case where R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted aryl groups is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. And phenyl groups are more preferred. Moreover, the substituent chosen from said substituent group is mentioned as a substituent in case an aryl group has a substituent.

When R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted heterocyclic groups, a triazine group, a thiazolyl group, a benzothiazolyl group or a thiadiazolyl group is preferable as a heterocyclic group. When the heterocyclic group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent group, and a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group are preferable.

When R ¹⁰¹ and R ¹⁰² are a substituted or unsubstituted alkylsulfonyl group, the alkylsulfonyl group having 1 to 6 carbon atoms is preferable, and the alkylsulfonyl group having 1 to 3 carbon atoms is preferable. The group is more preferred, and the methylsulfonyl group is more preferred. Moreover, the substituent selected from said substituent group is mentioned as a substituent in case an alkylsulfonyl group has a substituent.

The arylsulfonyl group in the case where R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted arylsulfonyl groups is preferably an arylsulfonyl group having 6 to 14 carbon atoms, and is an arylsulfonyl group having 6 to 10 carbon atoms. The group is more preferred, and the phenylsulfonyl group is more preferred. When the arylsulfonyl group has a substituent, examples of the substituent include those selected from the above-mentioned substituent group, and a carboxyl group is particularly preferable.

The alkoxycarbonyl group in the case where R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted alkoxycarbonyl groups is preferably represented by —COOR ²⁰¹ . Here, R ²⁰¹ is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an isopropyl group. Moreover, the substituent chosen from said substituent group is mentioned as a substituent in case an alkoxycarbonyl group has a substituent.

The aryloxycarbonyl group in the case where R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted aryloxycarbonyl groups is preferably represented by —COOR ²⁰² . Here, R ²⁰² is an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. When the aryloxycarbonyl group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent group, and a nitro group is particularly preferable.

When R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted monoalkylaminocarbonyl groups, the monoalkylaminocarbonyl group is preferably represented by -CONHR ²⁰³ . Here, R ²⁰³ is an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group. An ethyl group, an isopropyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group and a cyclohexyl group are more preferable, and an isopropyl group is particularly preferable. When the monoalkylaminocarbonyl group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent groups, and a phenyl group, a carboxyl group, a substituted or unsubstituted amino group and a hydroxyl group are particularly preferable. preferable.

When R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted dialkylaminocarbonyl groups, the dialkylaminocarbonyl group is preferably represented by —CONR ²⁰⁴ R ²⁰⁵ . Here, R ²⁰⁴ and R ²⁰⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an isopropyl group. When the dialkylaminocarbonyl group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent groups, and a carboxyl group and an alkyloxycarbonyl group (preferably having a carbon number of 2 or more and 6 or less) Particularly preferred is an alkyloxycarbonyl group, more preferably an ethyloxycarbonyl group.

When R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted monoarylaminocarbonyl groups, the monoarylaminocarbonyl group is preferably represented by —CONHR ²⁰⁶ . Here, R ²⁰⁶ is an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specifically, a phenyl group, a biphenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. When the monoarylaminocarbonyl group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent groups, and a carboxyl group, a hydroxyl group, a phosphono group, an alkoxy group (preferably having a carbon number of 1) Above, 6 or less alkoxy groups, more preferably cyclohexyloxy groups) are particularly preferable.

When R ¹⁰¹ and R ¹⁰² are substituted or unsubstituted diarylaminocarbonyl groups, the diarylaminocarbonyl group is preferably represented by —CONR ²⁰⁷ R ²⁰⁸ . Here, R ²⁰⁷ and R ²⁰⁸ each independently represent an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. When the diarylaminocarbonyl group has a substituent, examples of the substituent include substituents selected from the above-mentioned substituent group.

R ¹⁰¹ and R ¹⁰² are each preferably a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted alkoxycarbonyl group from the viewpoint of chroma, light resistance and ozone resistance of printed matter , Substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, or substituted or unsubstituted A substituted diarylaminocarbonyl group, more preferably a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylamide A carbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, or a substituted or unsubstituted diarylaminocarbonyl group, particularly preferably a substituted or unsubstituted monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group Or a substituted or unsubstituted monoarylaminocarbonyl group, or a substituted or unsubstituted diarylaminocarbonyl group.

  By using the magenta dye (1-1) for the secondary color ink, the coloring property of the printed matter can be secured with a smaller content than in the prior art, that is, at a low solid content, and clogging in the discharge nozzle hardly occurs. Become.

  As described above, the content of the magenta dye (1-1) contained in the secondary color ink is 0.1% by mass or more and 2.4% by mass or less with respect to the total mass of the ink. Preferably, it is 1.0 mass% or more and 2.0 mass% or less. By setting the content of the magenta dye (1-1) in the above-mentioned range, it is possible to secure the coloring property and to suppress the increase of the ink viscosity and the drying of the ink in the discharge nozzle and the like.

  Examples of yellow dyes having a symmetrical structure and a maximum absorption wavelength other than the range of 500 nm to 560 nm, which are used for secondary color inks, include, for example, general formula (2-1), general formula (2) The compound etc. which are represented by -2) are mentioned, 1 or more types in these are used. In addition, the yellow dye may include a yellow dye whose basic skeleton has a symmetrical structure other than the above as long as the object of the present invention can be achieved.

（一般式（２−１）において、Ｒ_Y1、Ｒ_Y2、Ｙ₁、およびＹ₂は、１価の基であり、Ｘ₁、Ｘ₂は、それぞれ独立にハメットのδｐ値０．２０以上の電子吸引性基である。Ｚ₁、Ｚ₂はそれぞれ独立に、水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアラルキル基、置換または無置換のアリール基、置換または無置換のヘテロ環基である。Ｍは、水素原子またはカチオンである。）

(In the general formula (2-1), R _Y1 , R _Y2 , Y ₁ and Y ₂ are monovalent groups, and X ₁ and X ₂ each independently have a Hammett δp value of 0.20 or more. Z ₁ and Z ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl Group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, and M is a hydrogen atom or a cation)

（一般式（２−２）において、Ｑはハロゲン原子である。Ｍは、水素原子、アルカリ金属、ＮＨ₄である。ｘ１は２以上、４以下の整数であり、ｙ１は１以上、３以下の整数である。）

(In the general formula (2-2), Q is a halogen atom. M is a hydrogen atom, an alkali metal, or NH _4. x1 is an integer of 2 or more and 4 or less, and y1 is 1 or more and 3 or less. Is an integer of

  Specific examples of such yellow dyes include C.I. I. (Color Index Generic Name) Direct Yellow 86, 132, 173, C.I. I. Acid Yellow 38, 42, 56, 87, C.I. I. Reactive yellow 84, 208, HEXL and the like.

  The mass ratio of the magenta dye (1-1) to the yellow dye, when the yellow dye is 1, is preferably 1.25 or more and 3.00 or less. According to this, when the mass of the yellow dye is 1.25 or more times the mass of the magenta dye (1-1), color reproducibility can be improved. When the mass of the yellow dye is 3.00 or less times the mass of the magenta dye (1-1), the color reproducibility can be further improved, and a secondary color ink which is less likely to cause clogging is further formed. Can be provided.

  As a cyan dye used for secondary color ink, the dye basic skeleton has a symmetrical structure and the maximum absorption wavelength is not in the range of 500 nm to 560 nm, a general formula (3-1), a general formula (3-2) And the like, and one or more of them are used. In addition, the cyan dye may include a cyan dye other than the above having a symmetrical structure as long as the object of the present invention can be achieved.

（一般式（３−２）において、破線で表される環Ａ₁，Ａ₂，Ａ₃，Ａ₄は、それぞれ独立にポルフィラジン環に縮環したベンゼン環または６員環の含窒素複素芳香環であり、含窒素複素芳香環の個数は、平均値で０．００を超えて３．００以下であり、残りはベンゼン環である。Ｒ₁は、炭素数が２以上、１２以下のアルキレン基である。Ｘは、置換基として、スルホ基、カルボキシ基、リン酸基、スルファモイル基、カルバモイル基、ヒドロキシ基、炭素数が１以上、６以下のアルコキシ基、アミノ基、炭素数が１以上、４以下の、モノアルキルアミノ基またはジアルキルアミノ基、炭素数が６以上、１０以下の、モノアリールアミノ基またはジアリールアミノ基、炭素数が１以上、３以下のアルキルカルボニルアミノ基、ウレイド基、炭素数が１以上、６以下のアルキル基、ニトロ基、シアノ基、ハロゲン原子、炭素数が１以上、６以下の、アルキルスルホニル基またはアルキルチオ基よりなる群から選択される１種類または２種類以上の置換基を有してもよい、スルホアニリノ基、カルボキシアニリノ基、ホスホノアニリノ基、スルホナフチルアミノ基、カルボキシナフチルアミノ基またはホスホノナフチルアミノ基である。Ｒは、水素原子、スルホ基、カルボキシ基、リン酸基、スルファモイル基、カルバモイル基、ヒドロキシ基、炭素数が１以上、６以下のアルコキシ基、アミノ基、炭素数が１以上、６以下の、モノアルキルアミノ基またはジアルキルアミノ基、モノアリールアミノ基、ジアリールアミノ基、炭素数が１以上、３以下のアルキルカルボニルアミノ基、ウレイド基、炭素数が１以上、６以下のアルキル基、ニトロ基、シアノ基、ハロゲン原子、炭素数が１以上、６以下のアルキルスルホニル基、またはアルキルチオ基である。基Ｆは、フェニル基または６員含窒素複素芳香環基であり、ｘ２は、炭素数が１以上、６以下のアルキレン基であり、ｂは平均値で０．００以上、３．９０未満であり、ｃは平均値で０．１０以上、４．００未満であり、かつｂおよびｃの和は、平均値で１．００以上、４．００未満である。）

(In the general formula (3-2), the rings A ₁ , A ₂ , A ₃ and A ₄ represented by broken lines are each independently a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring fused to a porphyrazine ring The number of nitrogen-containing heteroaromatic rings is, on average, more than 0.00 and not more than 3.00, and the remainder is a benzene ring R ₁ is an alkylene having 2 or more and 12 or less carbon atoms X is a substituent such as a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an amino group, 1 or more carbon atoms A monoalkylamino group or dialkylamino group having 4 or less carbon atoms, a monoarylamino group or a diarylamino group having 6 to 10 carbon atoms, an alkylcarbonylamino group having 1 to 3 carbon atoms and 3 or less carbon atoms, a ureido group, Charcoal One or more selected from the group consisting of an alkyl group having a prime number of 1 or more and 6 or less, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group or an alkylthio group having 1 or more and 6 or less carbon atoms A sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group or a phosphononaphthylamino group which may have a substituent, R represents a hydrogen atom, a sulfo group, a carboxy group, Phosphoric acid group, sulfamoyl group, carbamoyl group, hydroxy group, alkoxy group having 1 to 6 carbon atoms, amino group, monoalkylamino group or dialkylamino group having 1 to 6 carbon atoms, monoarylamino Group, a diarylamino group, an alkylcarbonylamino group having 1 or more and 3 or less carbon atoms, Id group, an alkyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group having 1 to 6 carbon atoms, or an alkylthio group F is a phenyl group or 6-membered nitrogen-containing heteroaromatic ring group, x 2 is an alkylene group having 1 to 6 carbon atoms, b is an average of 0.00 to less than 3.90, and c is an average 0.10 or more and less than 4.00, and the sum of b and c is 1.00 or more and less than 4.00 on average)

  Specific examples of such cyan dyes include C.I. I. Direct Blue 10, 12, 15, 106, 151, 152, 158, 162, 164, 166, 167, 190, 199, 231, C.I. I. Reactive blue 171, 204, C.I. I. Acid Blue 104 and the like.

  The mass ratio of the magenta dye (1-1) to the cyan dye is preferably 1.00 or more and 1.50 or less, where 1 is the cyan dye. According to this, color reproducibility can be improved by setting the mass of the cyan dye to 1.00 times or more of the mass of the magenta dye (1-1). When the mass of the cyan dye is 1.50 times or less of the mass of the magenta dye (1-1), the color reproducibility can be further improved, and the secondary color ink which is less likely to cause clogging is obtained. Can be provided.

  In the present embodiment, the dye used to mix with the magenta dye (1-1) to form a secondary color ink is not limited to the above. If the basic skeleton of the dye has a symmetrical structure and the maximum absorption wavelength is outside the range of 500 nm to 560 nm, dyes other than the above may be used.

  Specifically as such a dye, for example, C.I. I. Direct Brown 106, 184, C.I. I. Acid Brown 13, C.I. I. Direct Black 19, 29, 122, C.I. I. Acid Black 41, C.I. I. Reactive red 120, 141, and the like.

  The basic color inks of black ink, cyan ink, magenta ink, and yellow ink may be combined with the secondary color ink and used as an ink set. As the ink set, one or more of the above-described secondary color inks and one or more of the basic color inks may be combined. It is possible to use a well-known color material for basic color ink. Known colorants include dyes or pigments. Further, as components other than the color material contained in the basic color ink, components used for the secondary color ink described below can be adopted.

(water)
Water is the main medium (solvent) of the ink. When the ink is attached to the recording medium and printing is performed, the water evaporates and scatters from the recording medium by drying. As water, for example, pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, distilled water, and water from which ionic impurities such as ultrapure water are removed as much as possible can be used. In addition, if water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, the generation of mold and bacteria can be suppressed when the ink is stored for a long time. The content of water contained in the ink is not particularly limited, but is, for example, 45% by mass or more, preferably 50% by mass to 95% by mass, and more preferably 55% by mass to 90% by mass, based on the total mass of the ink. It is preferable to set it as the following.

(Organic solvent)
An organic solvent may be added to the ink. By adding an organic solvent, it is possible to control the physical properties of the ink such as viscosity and surface tension, and the behavior of drying, permeation, etc. when it is attached to the recording medium. Examples of the organic solvent include 2-pyrrolidones, 1,2-alkanediols, polyhydric alcohols, glycol ethers and the like. These can be used alone or in combination of two or more.

  2-Pyrrolidone refers to a compound having a 2-pyrrolidone skeleton. As 2-pyrrolidones, for example, in addition to 2-pyrrolidone having no substituent, a substituent such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and the like The compound which has is used. The substituent in the 2-pyrrolidone skeleton is preferably an organic group having 1 to 5 carbon atoms, such as a saturated or unsaturated hydrocarbon group. Among these, it is more preferable to use 2-pyrrolidone which is excellent in the storage stability of the ink and the effect of suppressing the generation of aggregates.

  The content in the case of adding 2-pyrrolidones is preferably 0.9% by mass or more and 8.1% by mass or less with respect to the total mass of the ink. More preferably, it is 1.0 mass% or more and 8.0 mass% or less. By setting the content of 2-pyrrolidones in the above range, it is possible to suppress the increase in the viscosity of the ink and to improve the ejection stability of the ink.

  Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol and the like. . The 1,2-alkanediols enhance the wettability of the ink to the recording medium and excel in the uniform wetting action. Therefore, it is possible to produce a printed matter with suppressed bleeding. The content of the 1,2-alkanediols is preferably 1% by mass or more and 20% by mass or less based on the total mass of the ink.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol, and 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl- 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, glycerin and the like. By adding polyhydric alcohols to the ink, it is possible to suppress the drying and solidification of the ink in the discharge nozzle of the ink jet head, and to reduce clogging and discharge failure of the discharge nozzle. It is preferable that content in the case of adding polyhydric alcohols is 2 mass% or more and 20 mass% or less with respect to the total mass of ink. In addition, polyhydric alcohol which is solid at 20 ° C. also has the same function as polyhydric alcohol of organic solvent, and may be used in the same manner. Examples of polyhydric alcohols solid at 20 ° C. include trimethylolpropane and the like.

  Examples of glycol ethers include alkylene glycol monoethers and alkylene glycol diethers.

  As an alkylene glycol monoether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

  As alkylene glycol diether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol diethylene glycol Chirueteru, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

  By adding glycol ethers to the ink, it is possible to adjust the wettability to the recording medium and the permeation speed, so that it is possible to form an image, a pattern, etc. clearly. It is preferable that content in the case of adding glycol ethers is 0.05 mass% or more and 6 mass% or less with respect to the total mass of ink.

  The organic solvents described above may be used as a mixture of two or more. In that case, the total content of the organic solvent in the ink is 0.2% by mass or more and 30.0% by mass or less, preferably 0.4% by mass or more and 20.0% or less, based on the total mass of the ink. It is mass% or less, More preferably, they are 0.5 mass% or more and 15.0 mass% or less. By setting the total content of the organic solvent in the above range, the increase in viscosity of the ink can be suppressed, the behavior (penetration and wetting spread) when it is attached to the recording medium, and the ejection stability at the time of printing can be improved. And so on.

(Surfactant)
A surfactant may be added to the ink. The surfactant has a function of reducing the surface tension of the ink to increase the permeability to the recording medium. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and at least one of them can be employed.

  When the surfactant is added to the ink, the content is 0.01% by mass or more and 3.00% by mass or less based on the total mass of the ink. The content is preferably 0.05% by mass or more and 2.00% by mass or less, more preferably 0.10% by mass or more and 1.00% by mass or less, and still more preferably 0.20% by mass or more. It is 0.50 mass% or less. By setting the content of the surfactant in the above range, it is possible to suppress foaming and ensure discharge stability at the time of printing and to improve the wetting and spreading (wettability) of the ink when it adheres to the recording medium. it can.

  As the nonionic surfactant, an acetylene glycol surfactant, a fluorine surfactant, a silicone surfactant or the like can be used. By using these surfactants, the wettability to the recording medium can be improved with a relatively small content.

  The acetylene glycol surfactant is not particularly limited, and examples thereof include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5- Alkylene oxide adduct of decyne-4,7-diol, 2,4-dimethyl-5-decyn-4-ol, alkylene oxide adduct of 2,4-dimethyl-5-decyn-4-ol, 3,6- Examples include alkylene oxide adducts such as dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexyn-3ol, 2,4-dimethyl-5-hexyn-3-ol and the like.

  A commercial item may be used as such an acetylene glycol type surfactant. For example, Surfynol (registered trademark) 104, 104 E, 104 H, 104 A, 104 BC, 104 DPM, 104 PA, 104 PG-50, 104 S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF 37, CT 111, CT121, CT131, CT136, TG, GA, DF110D (trade name, Air Products and Chemicals, Inc.), Olfin (registered trademark) B, Y, P, A, STG, SPC, E1004, E1010, PD-001 , PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (trade names, Nisshin Chemical Industries, Ltd.), Acetylenol (registered trademark) E00, E00P, E40, E100 (trade names, Kawaken Fine Chemicals Co., Ltd.

  As a fluorochemical surfactant, a commercial item can be employ | adopted, for example, Megafuck (trademark) F-479 (a brand name, DIC company), BYK-340 (a trade name, BYK company) etc. are mentioned.

  The silicone surfactant is not particularly limited, but a polysiloxane compound can be employed. The polysiloxane compound is not particularly limited, and examples thereof include polyether-modified organosiloxanes. As a commercial item of polyether modified organosiloxane, for example, BYK-302, 306, 307, 333, 341, 345, 346, 347, 348 (trade name, BYK company), KF-351A, 352A, 353, 354L. 355A, 615A, 945, 640, 642, 643, 6020, 6011, 6012, 6015, 6017, X-22-4515 (all trade names, Shin-Etsu Chemical Co., Ltd.), and the like.

  As the anionic surfactant, for example, higher fatty acid salt, soap, α-sulfo fatty acid methyl ester salt, alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, monoalkyl phosphate ester salt, α-olefin Sulfonates, alkyl naphthalene sulfonates, naphthalene sulfonates, alkane sulfonates, polyoxyethylene alkyl ether sulfates, sulfosuccinates, polyoxyalkylene glycol alkyl ether phosphates and the like.

  As the cationic surfactant, for example, quaternary ammonium salt compounds such as alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, and amine salt compounds such as N-methylbishydroxyethylamine fatty acid ester hydrochloride It can be mentioned.

  The amphoteric surfactant includes, but is not particularly limited to, amino acid compounds such as alkylamino fatty acid salts.

  The surfactants described above may be used alone or in combination of two or more.

(Other ingredients)
The ink may contain, as other components, various additives such as pH adjusters, preservatives, fungicides, antioxidants, chelating agents, fixing agents (resin fine particles) and the like.

[Preparation of ink]
The ink of the present embodiment can be prepared by mixing the above-described components in an arbitrary order, filtering as necessary, and removing impurities and foreign matter. As a method of mixing each component, a method of sequentially adding, stirring, and mixing materials in a container equipped with a stirring device such as a mechanical stirrer or a magnet stirrer is used. Methods of filtration include centrifugal filtration, filter filtration and the like.

[Physical properties of ink]
The surface tension of the ink at 25 ° C. is preferably 10 mN / m or more and 40 mN / m or less. More preferably, it is 20 mN / m or more and 40 mN / m or less, and still more preferably 20 mN / m or more and 35 mN / m or less. By setting the surface tension at 25 ° C. to the above-mentioned range, the ejection stability of the ink from the ejection nozzle is improved when printing is performed. Moreover, a high definition image etc. can be formed on a printed matter. The surface tension of the ink may be measured, for example, by immersing a part of the platinum plate in the ink at 25 ° C. using an automatic surface tension meter CBVP-Z (Kyowa Interface Science Co., Ltd.) It is possible.

  From the same viewpoint as the surface tension, the viscosity of the ink at 20 ° C. is preferably 2 mPa · s (milli pascal second) or more and 15 mPa · s or less. More preferably, it is 2 mPa · s or more and 10 mPa · s or less, and still more preferably 3 mPa · s or more and 6 mPa · s or less. The viscosity of the ink can be measured, for example, using a viscoelasticity tester MCR-300 (Pysica). Specifically, it is measured by adjusting the temperature of the ink to 20 ° C., raising the Shear Rate from 10 to 1000, and reading the viscosity at a Shear Rate of 200.

[Ink jet recording apparatus]
The inkjet recording apparatus will be described with reference to FIG. The inkjet recording apparatus is an apparatus that performs printing by causing droplets to land on a recording medium or the like by an inkjet method that discharges ink droplets. FIG. 1 is a schematic perspective view showing an example of the ink jet recording apparatus. In the present embodiment, as an inkjet recording apparatus, an on-carriage type printer in which an ink cartridge is mounted on a carriage will be described as an example. In addition, in FIG. 1, in order to make each member into a recognizable size, the scale of each member is made different from the actual scale.

  The printer 1 shown in FIG. 1 is a so-called serial printer. The serial printer is a printer in which an inkjet head is mounted on a carriage that moves in a predetermined direction, and printing is performed while the inkjet head moves as the carriage moves.

  As shown in FIG. 1, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The carriage 4 mounts the ink jet head 3, and the ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, 7 f for storing the ink supplied to the ink jet head 3 are attachable and detachable.

  The main scanning mechanism 5 has a timing belt 8 connected to the carriage 4, a motor 9 for driving the timing belt 8, and a guide shaft 10. The guide shaft 10 is bridged in the scanning direction (main scanning direction) of the carriage 4 as a support member of the carriage 4. The carriage 4 is driven by a motor 9 through a timing belt 8 and can be reciprocated along a guide shaft 10. Thus, the main scanning mechanism 5 has a function of reciprocating the carriage 4 in the main scanning direction.

  The platen roller 6 has a function of transporting the recording medium 2 on which printing is to be performed, in the sub-scanning direction (length direction of the recording medium 2) orthogonal to the main scanning direction. Therefore, the recording medium 2 is conveyed in the sub scanning direction. Further, the carriage 4 on which the ink jet head 3 is mounted can be reciprocated in the main scanning direction substantially coincident with the width direction of the recording medium 2, and the ink jet head 3 can move in the main scanning direction and the sub scanning direction with respect to the recording medium 2. Relative scanning is possible in the scanning direction.

  The ink cartridges 7a, 7b, 7c, 7d, 7e and 7f are six independent ink cartridges. The ink cartridges 7a, 7b, 7c, 7d, 7e, 7f can store a plurality of types of basic color inks of black ink, cyan ink, magenta ink, yellow ink, and the secondary color ink of the present embodiment. These inks are stored separately from the ink cartridge 7a to the ink cartridge 7f, and can be used in arbitrary combinations. Although the number of ink cartridges is six in FIG. 1, the number is not limited to this. At the bottom of each of the ink cartridges 7a, 7b, 7c, 7d, 7e, 7f, a supply port (not shown) for supplying the ink stored in each ink cartridge to the ink jet head 3 is provided.

  The inkjet head 3 has a nozzle surface (not shown) on the surface facing the recording medium 2. On the nozzle surface, a nozzle row (not shown) composed of a plurality of discharge nozzles (not shown) is individually disposed corresponding to each color ink. The respective color inks are supplied from the respective ink cartridges to the inkjet head 3 and are ejected as droplets from the ejection nozzle by an actuator (not shown) in the inkjet head 3. The ejected ink droplets land on the recording medium 2, and an image, text, a pattern, a color, etc. are formed on the recording medium 2.

  Here, in the inkjet head 3, a piezoelectric element is used as an actuator (driving means), but the invention is not limited to this method. For example, an electromechanical conversion element that displaces a diaphragm as an actuator by electrostatic adsorption, or an electrothermal conversion element that discharges ink as droplets by air bubbles generated by heating may be used.

  In the present embodiment, the on-carriage type printer 1 is described as an example of the inkjet recording apparatus, but the present invention is not limited to this. For example, the printer may be an off-carriage type printer in which an ink storage container such as an ink cartridge is not mounted on a carriage. Further, the inkjet recording apparatus is not limited to the above-described serial printer, and is a line head printer in which the inkjet head is formed wider than the width of the recording medium 2 and printing is performed without moving the inkjet head. May be

  The recording medium 2 is appropriately selected according to the application of the printed matter and the type of ink used for printing. As the recording medium 2 in the case of using the water-based ink as in this embodiment, for example, plain paper such as electrophotographic paper having high permeability of water-based ink, ink jet paper (ink jet paper), art paper, coated paper, cast Examples thereof include papers such as paper, and fabrics using natural fibers or chemical fibers. Since the ink of the present embodiment is a water-based dye ink, it can be suitably used for plain paper, inkjet paper (inkjet-dedicated paper), and the like among the recording media 2 described above.

[Ink jet recording method]
Next, an inkjet recording method using the printer 1 and the ink will be described.

  The ink jet recording method of the present embodiment includes the step of adhering the ink to the recording medium 2. In the process, ink droplets (droplets of ink) are ejected from the inkjet head 3 of the printer 1 to the recording medium 2. At this time, ink droplets are ejected intermittently at a predetermined timing and with a predetermined mass to cause the ink droplets to land and adhere to the recording medium 2, and a design of a desired image, characters, patterns, colors, etc. It is printed. A printed matter is produced by this.

  As described above, according to the secondary color ink of the present embodiment, the following effects can be obtained.

  It is possible to provide a secondary color ink in which the color reproducibility and color development of the printed matter are improved as compared with the prior art, and clogging in the discharge nozzle is less likely to occur.

  Since the color developability of the magenta dye (1-1) is high, the color developability can be secured at a content lower than that of the prior art, and an ink in which clogging does not easily occur in the inkjet head 3 (discharge nozzle) can be provided. Moreover, ozone resistance, moisture resistance, etc. in printed matter can be improved by using the magenta dye (1-1).

  When the magenta dye (1-1) and the yellow dyes represented by the general formula (2-1) and the general formula (2-2) are used in combination, the color gamut of the yellow region is expanded and color reproducibility is improved. It can be improved.

  When the magenta dye (1-1) and the cyan dyes represented by the general formula (3-1) and the general formula (3-2) are used in combination, the color gamut of the cyan region is expanded, and the color reproducibility is improved. It can be improved.

  By mixing two or more dyes having a symmetrical structure in the basic skeleton, the dye molecules interact with each other, the gaps between the dye molecules are reduced, and the association is improved. This highly associative ink is less susceptible to ozone molecules than an ink composition using a less associative dye. Therefore, the decomposition of the dye molecule by the ozone molecule is suppressed, and it is possible to provide the ink in which the ozone resistance performance of the printed matter is improved.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the following evaluations, the temperature was 25 ° C., and the relative humidity was 40%, unless otherwise noted.

[Preparation of Ink Composition]
The compositions of the inks of Examples and Comparative Examples are shown in Table 1. The ink can be prepared by mixing the components described in Table 1 in an arbitrary order, mixing for 30 minutes or more, filtering as necessary, and removing impurities and foreign matter. As a method of mixing each component, a method of sequentially adding, stirring, and mixing materials is used in a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer. As a method of filtration, centrifugal filtration, filter filtration, etc. can be adopted. In addition, the unit of the numerical value in Table 1 is "mass%."

  Glycerin and triethylene glycol monobutyl ether (abbreviated as “TEGmBE” in Table 1) were used as the organic solvent. As surfactants, Orphin (registered trademark) E1010 (trade name, Nisshin Chemical Industry Co., Ltd.) and Surfynol (registered trademark) 104 PG-50 (trade name, Air), both of which are nonionic (acetylene glycol based) surfactants. Products and Chemicals, Inc. (in the table, "104PG50") was used. The ion exchange water was adjusted and added so that the total mass of each ink of the example and the comparative example would be 100.0% by mass.

  Here, the dyes described below were used for the inks of Examples and Comparative Examples. As a magenta dye (1-1), a magenta dye (a) represented by the following general formula (a), a magenta dye (b) represented by the following general formula (b) as a magenta dye (1-2) As a magenta dye (1-3), a magenta dye (c) represented by the following general formula (c) was used.

  Further, as the yellow dye (2-1), a yellow dye (d) represented by the following general formula (d), and as the yellow dye (2-2), a yellow dye (e) represented by the following general formula (e) Was used.

  In addition, as the cyan dye (3-1), a cyan dye (f) represented by the following general formula (f) and a cyan dye (g) represented by the following general formula (g) as the cyan dye (3-2) Was used.

  Here, the magenta dye (b) and the magenta dye (c) will be described. At least one of magenta dyes (1-2) having no symmetrical structure in the basic skeleton and yellow dyes and cyan dyes having a dye basic skeleton having a symmetrical structure and a maximum absorption wavelength other than the range of 500 nm to 560 nm And are mixed to prepare a secondary color ink composition. In addition, the magenta dye (1-3) has a symmetrical basic structure, but has an anthrapyridine skeleton and has a low color forming property. The magenta dye (1-3) is mixed with at least one of a yellow dye and a cyan dye having a symmetrical dye basic structure and a maximum absorption wavelength outside the range of 500 nm to 560 nm. The next color ink composition is prepared.

（一般式（ｇ）において、破線で表される環Ａ₁，Ａ₂，Ａ₃は、それぞれ独立にポルフィラジン環に縮環したベンゼン環または６員環の含窒素複素芳香環であり、含窒素複素芳香環の個数は、平均値で０．００を超えて３．００以下であり、残りはベンゼン環である。ｂは平均値で０．００以上、３．９０未満であり、ｃは平均値で０．１０以上、４．００未満であり、かつｂおよびｃの和は、平均値で１．００以上、４．００未満である。）

(In the general formula (g), the rings A ₁ , A ₂ and A ₃ represented by broken lines each independently represent a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring fused to a porphyrazine ring; The number of nitrogen heteroaromatic rings is more than 0.00 and not more than 3.00 on average, and the remainder is a benzene ring, b is not less than 0.00 and less than 3.90 on average, and c is The average value is 0.10 or more and less than 4.00, and the sum of b and c is 1.00 or more and less than 4.00.)

[Evaluation test of color reproducibility]
The c * value of each ink composition (Examples 1 to 8 and Comparative Examples 1 to 5) was evaluated as an index of color reproducibility. Specifically, first, a diluted solution of each ink with water was prepared to measure spectral characteristics. The ultraviolet visible near infrared spectrophotometer V-770 (JASCO Corporation) was used for the measurement of a spectral characteristic. At the time of measurement, it is dissolved and diluted to a mass ratio of 1000 using water such as ion-exchanged water to prepare a diluted aqueous solution of the compound, which is filled in a 1 cm optical path quartz cell and measured in transmission mode Did. The L * a * b * values of the ink composition were determined from the measured spectral characteristics using a color analysis program attached to the spectrophotometer. The c * value was calculated as described above, and determined according to the following criteria, and the evaluation results are shown in Table 2.
Evaluation A: c * value of L * a * b * color system is 30 or more.
Evaluation B: c * value of L * a * b * color system is 20 or more and less than 30.
Evaluation C: The c * value of the L * a * b * color system is less than 20.

[Production of printed matter for evaluation]
The ink cartridge filled with the ink of each of the example and the comparative example was attached to an ink jet printer EP-10VA (trade name, manufactured by Seiko Epson Corporation). Next, in a mode without color correction, solid printing was performed on photographic paper (ink jet paper: Seiko Epson Corporation) under printing conditions of image resolution 600 dpi (Dots Per inch). After drying this printed matter for 3 hours, it was made into the printed matter for evaluation.

[Coloring evaluation]
The OD (Optical Density) value of the printed matter using each ink was evaluated as an index of color development. Using a colorimeter i1 (trade name, manufactured by X-Rite Co., Ltd.), the OD value of the area in which each ink was solidly printed was measured under the measurement conditions of no light source filter, light source D50, and 2 view angle. Also, the numerical values were evaluated according to the following criteria, and the results are shown in Table 2.
Evaluation A: OD value is 1.90 or more.
Evaluation B: OD value is 1.70 or more and less than 1.90.
Evaluation C: OD value is less than 1.70.

[Ozone resistance evaluation]
As a measure of ozone resistance, the printed matter was exposed in an atmosphere containing ozone, and the change in OD value was measured. Specifically, the printed matter whose initial OD value was used for the evaluation of the color development was exposed to an atmosphere of 23 ° C., a relative humidity of 50%, and an ozone concentration of 5 ppm. The printed matter was taken out at regular intervals, the OD was measured in the same manner as in the evaluation of color development, and exposure was repeated again to investigate the tendency of the OD value to decrease. The data was evaluated for the total exposure time under an atmosphere containing ozone (hereinafter, also simply referred to as "exposure time") and ROD according to the following criteria, and the results are shown in Table 2 as the ozone resistance evaluation. .
Evaluation A: ROD does not decrease to 70% by 80 hours after the exposure time.
Evaluation B: The ROD decreases to 70% when the exposure time is 64 hours or more and less than 80 hours.
Evaluation C: The ROD decreases to 70% when the exposure time is less than 64 hours.

[Humidity evaluation]
A pattern including characters (characters printed with the ink and white characters surrounded by the ink) was printed by the printing method. The obtained printed matter was allowed to stand in a constant temperature bath set to a temperature of 40 ° C. and a relative humidity of 85% for 7 days, and the tendency of bleeding in the above pattern was visually examined. The data were evaluated according to the following criteria, and the results are shown in Table 2 as the moisture resistance evaluation.
Evaluation A: Bleeding in the pattern is hardly observed.
Evaluation B: Bleeding in the pattern is observed, and the character outline is broken.
Evaluation C: Bleeding in the pattern is observed, and the whole of the letter-weighted and white-colored letters are colored.

[Clogging recovery evaluation]
The clogging recovery in the discharge nozzle was evaluated. Specifically, the ink cartridge filled with each ink was attached to an inkjet printer EP-10VA (trade name, manufactured by Seiko Epson Corporation). Then, after head cleaning was performed, a nozzle check pattern was printed to confirm that all the discharge nozzles were discharging normally. The ink jet printer was left in a thermostatic chamber with a temperature of 40 ° C. and a relative humidity of 25% for 35 days. After the above-mentioned standing, a nozzle check pattern was printed to observe the state of discharge. In the case where a discharge failure such as a non-discharge nozzle, a dot deviation, thinning, or thickening occurred, head cleaning was performed, and head cleaning was repeated until all the discharge nozzles discharged normally. The number of head cleanings required to recover all the discharge nozzles was recorded. The data was evaluated according to the following criteria, and the results are listed in Table 2 as clogging recovery.
Evaluation A: A discharge failure does not occur, or the number of times of head cleaning is one.
Evaluation B: The number of times of head cleaning is two or more and five or less.
Evaluation C: The number of head cleanings is six or more.

  As shown in Table 2, in the color reproducibility evaluation, B, which corresponds to the “suitable” level in Example 2, Example 5, Example 7, and Example 8, is B evaluation, and the other examples are “suitable” levels. It became an A rating equivalent to This shows that the color reproducibility is improved in all the examples.

  In the color development evaluation, Example 2, Example 5, and Example 6 became B evaluation corresponded to a "suitable" level, and other Examples became A evaluation corresponded to a "suitable" level. This shows that the color developability is improved in all the examples.

  In ozone resistance evaluation, Example 2 became B evaluation corresponded to a "suitable" level, and other Examples became A evaluation corresponded to a "suitable" level. This shows that the ozone resistance of the printed material is improved in all the examples.

  In the moisture resistance evaluation, Example 5 and Example 6 were B evaluation equivalent to the "suitable" level, and other examples were A evaluation equivalent to the "suitable" level. This shows that the moisture resistance of the printed matter is improved in all the examples.

  In the clogging recovery evaluation, Example 3 and Example 4 were B evaluation equivalent to the "suitable" level, and other examples were A evaluation equivalent to the "suitable" level. This shows that the clogging recovery is improved in all the examples.

  On the other hand, in Comparative Example 2, Comparative Example 4, and Comparative Example 5, since the magenta dye (1-3) having the target structure but having a low color forming property is used, the color reproducibility evaluation and the color forming evaluation of the printed matter It became C evaluation corresponding to a "non-suitable" level, and it turned out that it is difficult to secure color reproducibility and color developability of printed matter.

  Further, in Comparative Example 3, since the content of the magenta dye (1-3) was 6.00% by mass, the color developability was evaluated as B. However, this is an ink composition having a solid content concentration (content of the dye) capable of securing the color forming property, and the clogging recovery evaluation was C evaluation corresponding to the “unsuitable” level. It turned out that it is difficult to ensure clogging recovery by this.

  In Comparative Example 1, since the magenta dye (1-2) having no target structure is used, the ozone resistance evaluation is a C evaluation corresponding to the “unsuitable” level, and it is found that it is difficult to secure the ozone resistance. The

  DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Recording medium, 3 ... Ink jet head, 4 ... Carriage, 5 ... Main scanning mechanism, 6 ... Platen roller, 7a, 7b, 7c, 7d, 7e, 7f ... Ink cartridge, 8 ... Timing belt, 9 ... motor, 10 ... guide shaft.

Claims (6)

A magenta dye represented by the following general formula (1-1),
An inkjet ink composition comprising one or more of a yellow dye and a cyan dye, wherein the dye basic skeleton has a symmetrical structure and has a maximum absorption wavelength outside the range of 500 nm to 560 nm.

(In the general formula (1-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and R ¹⁰¹ and R ¹⁰² each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted Aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl Group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group Substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.)   The content of the magenta dye represented by the general formula (1-1) is in the range of 0.1% by mass or more and 2.4% by mass or less based on the total mass of the inkjet ink composition. The inkjet ink composition according to 1. The inkjet ink composition according to claim 1 or 2, wherein the yellow dye contains one or more of yellow dyes represented by the following general formula (2-1) and the following general formula (2-2) object.

(In the general formula (2-1), R _Y1 , R _Y2 , Y ₁ and Y ₂ are monovalent groups, and X ₁ and X ₂ each independently have a Hammett δp value of 0.20 or more. Z ₁ and Z ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl Group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, and M is a hydrogen atom or a cation)

(In the general formula (2-2), Q is a halogen atom. M is a hydrogen atom, an alkali metal, or NH _4. x1 is an integer of 2 or more and 4 or less, and y1 is 1 or more and 3 or less. Is an integer of   The mass ratio of the magenta dye represented by the general formula (1-1) to the yellow dye is 1.25 or more and 3.00 or less, when the yellow dye is 1. Ink jet ink composition. The inkjet ink composition according to claim 1 or 2, wherein the cyan dye contains one or more of cyan dyes represented by the following general formula (3-1) and the following general formula (3-2). object.

(In the general formula (3-2), the rings A ₁ , A ₂ , A ₃ and A ₄ represented by broken lines are each independently a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring fused to a porphyrazine ring The number of nitrogen-containing heteroaromatic rings is, on average, more than 0.00 and not more than 3.00, and the remainder is a benzene ring R ₁ is an alkylene having 2 or more and 12 or less carbon atoms X is a substituent such as a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an amino group, 1 or more carbon atoms A monoalkylamino group or dialkylamino group having 4 or less carbon atoms, a monoarylamino group or a diarylamino group having 6 to 10 carbon atoms, an alkylcarbonylamino group having 1 to 3 carbon atoms and 3 or less carbon atoms, a ureido group, Charcoal One or more selected from the group consisting of an alkyl group having a prime number of 1 or more and 6 or less, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group or an alkylthio group having 1 or more and 6 or less carbon atoms A sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group or a phosphononaphthylamino group which may have a substituent, R represents a hydrogen atom, a sulfo group, a carboxy group, Phosphoric acid group, sulfamoyl group, carbamoyl group, hydroxy group, alkoxy group having 1 to 6 carbon atoms, amino group, monoalkylamino group or dialkylamino group having 1 to 6 carbon atoms, monoarylamino Group, a diarylamino group, an alkylcarbonylamino group having 1 or more and 3 or less carbon atoms, Id group, an alkyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, a halogen atom, an alkylsulfonyl group having 1 to 6 carbon atoms, or an alkylthio group F is a phenyl group or 6-membered nitrogen-containing heteroaromatic ring group, x 2 is an alkylene group having 1 to 6 carbon atoms, b is an average of 0.00 to less than 3.90, and c is an average 0.10 or more and less than 4.00, and the sum of b and c is 1.00 or more and less than 4.00 on average)   The mass ratio of the magenta dye represented by the general formula (1-1) to the cyan dye is, when the cyan dye is 1, 1.00 or more and 1.50 or less. Ink jet ink composition.

Images