JP2019163405A - Inkjet ink composition and ink set - Google Patents

Abstract

To provide an inkjet ink composition and an ink set which enhance gas resistance in a pale region having a low recording density recorded with a light magenta ink, and improve a discoloration balance when left in the environment.SOLUTION: The inkjet ink composition comprises a first dye, which is a compound represented by general formula (1), and a second dye; and has a maximum absorbance upon 1000-fold dilution from 0.10 to 0.80 inclusive. The ink set comprises a light magenta ink and a magenta ink.SELECTED DRAWING: None

Description

  The present invention relates to an inkjet ink composition and an ink set.

  The ink jet recording method is capable of recording high-definition images by supplying ink to a print head, ejecting ink droplets from the print head, and depositing the ink on a recording medium such as paper. Has made great progress. Among them, various studies have been made on improving the obtained image.

  For example, in Patent Document 1, a light ink composition (hereinafter also referred to as “light ink”) such as light magenta, light cyan, or light black is added to an ink set in cyan, magenta, and yellow inks that are basic colors. Discloses a technique for improving the gas resistance and graininess of an image.

JP 2011-195783 A

  However, since light ink has a low dye content in the composition, it tends to be decomposed by ozone gas, light, etc., and tends to have low weather resistance. In particular, since fading in light-colored areas with low recording density recorded using light magenta ink is faster than other areas with high recording density, the problem of fading balance easily lost when exposed to ozone gas is left. There is.

一般式（１）中、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及びＲ^２０は各々独立に
水素原子又は置換基を表し、Ｒ^１０１及びＲ^１０２は各々独立に置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のカルバモイル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、又は置換若しくは無置換のアルキルアリールアミノカルボニル基を表す。

一般式（２）中、Ａ^M１は、炭素数１もしくは２のアルキレン基、フェニレン基を含有する炭素数１もしくは２のアルキレン基又は下記一般式（３）で表される基を表し、Ｘ^M１は、アミノ基、ヒドロキシ基、塩素原子、又はスルホ基もしくはカルボキシ基で置換されたフェノキシ基を表す。

一般式（３）中、Ｒ^M１は、水素原子又はアルキル基を表す。 [Application Example 1]
One aspect of the inkjet ink composition according to the present invention is:
A first dye that is a compound represented by the following general formula (1) and a second dye that is a compound represented by the following general formula (2), and the maximum absorbance at 1000-fold dilution is 0. It is 10 or more and 0.80 or less.

In the general formula ^{(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, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Substituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted It represents a mono arylaminocarbonyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.

In the general formula (2), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following general formula (3), and X ^M1 Represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.

In General Formula (3), R ^M1 represents a hydrogen atom or an alkyl group.

[Application Example 2]
In application example 1,
The second dye may be a compound represented by the following general formula (4).

[Application Example 3]
In application example 1 or application example 2,
Content of the dye which is a compound represented by the said General formula (1) can be 0.1 to 1.2 mass% with respect to the total mass of an ink composition.

[Application Example 4]
In any one of Application Examples 1 to 3,
In the compound represented by the general formula (1), R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ can each independently represent an alkyl group having 1 to 6 carbon atoms.

[Application Example 5]
In any one of Application Examples 1 to 4,
It can be light magenta ink used with magenta ink.

[Application Example 6]
One aspect of the ink set according to the present invention is:
An ink set including light magenta ink and magenta ink,
The light magenta ink is the inkjet ink composition according to any one of Application Examples 1 to 5.

  A preferred embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described below. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

  Hereinafter, the inkjet ink composition and the ink set according to the present embodiment will be described in detail.

1. Inkjet ink composition An inkjet ink composition according to an embodiment of the present invention is a first dye that is a compound represented by the general formula (1) and a second compound that is a compound represented by the general formula (2). The maximum absorbance at 1000-fold dilution is 0.10 or more and 0.80 or less.

  Hereinafter, components contained in the inkjet ink composition according to the present embodiment (hereinafter also simply referred to as “ink”) and components that may be contained will be described.

  The ink-jet ink composition according to the present embodiment is a light magenta ink used together with magenta ink. In this case, the dye contained in the magenta ink and the dye contained in the light magenta ink are the same or different. It may be. In this specification, when the dye contained in the magenta ink is the same as the dye contained in the light magenta ink, the light magenta ink having the smaller dye content on a mass basis is used.

一般式（１）中、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及びＲ^２０は各々独立に水素原子又は置換基を表し、Ｒ^１０１及びＲ^１０２は各々独立に置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のアルキルスルホニル基、置換若しくは無置換のアリールスルホニル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、置換若しくは無置換のカルバモイル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、又は置換若しくは無置換のアルキルアリールアミノカルボニル基を表す。 1.1. 1st dye The inkjet ink composition which concerns on this embodiment contains the 1st dye which is a compound represented by following General formula (1). The dye represented by the general formula (1) may form a salt.

In the general formula ^{(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, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Substituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted It represents a mono arylaminocarbonyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.

  The first dye used in the ink-jet ink composition according to this embodiment is a compound represented by the above general formula (1), and is contained together with the second dye described later, so that the light resistance in a light color region where the recording density is low. Gasity can be improved.

  Hereinafter, the compound represented by the general formula (1) will be described. In addition, about the compound represented by General formula (1), description of paragraph number 0015-0084 of Unexamined-Japanese-Patent No. 2016-41801 is quoted.

  First, specific examples of the substituent used in the compound represented by the general formula (1) are defined as a substituent group A.

<Substituent group A>
Halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy 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, aryloxycarbonyl group, Job aryloxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, an ionic hydrophilic group mentioned as an example. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group.
The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, 2- Examples thereof include a chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, etc. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, 4 -N-dodecylcyclohexyl group and the like, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Removed monovalent groups such as bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] Octane-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups.
Preferred examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. Preferred examples of the cycloalkenyl group include Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, a 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group and the like. As the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a double bond A monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one of, for example, bicyclo [2,2,1] hept- - en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, or a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

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

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms, such as trimethylsilyloxy group and diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

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

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, or an N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as a methoxycarbonylamino group, ethoxycarbonylamino group, t-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, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, or Nn-. Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
As an alkylthio group, Preferably, a C1-C30 substituted or unsubstituted alkylthio group, for example, a methylthio group, an ethylthio group, n-hexadecylthio group, etc. are mentioned.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfur group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group or an ethylsulfinyl group. , Phenylsulfinyl group, p-methylphenylsulfinyl group and the like.

  The alkyl or arylsulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group or an ethylsulfonyl group. , Phenylsulfonyl group, p-methylphenylsulfonyl group and the like.

The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  Preferred examples of the alkoxycarbonyl group include substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as a phenylazo group or p-chlorophenylazo. Group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group and the like.

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

  Preferred examples of the phosphino group include substituted or unsubstituted phosphino groups having 0 to 30 carbon atoms such as a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group.
Particularly preferred are a sulfo group and a carboxyl group. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ions, alkali metal ions (for example, lithium ions, sodium ions, potassium ions) and organic compounds. Cation (for example, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, and ammonium salt are preferable, and sodium salt or mixed salt mainly composed of sodium salt Are more preferred, and the sodium salt is most preferred.

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

<Compound represented by the general formula (1)>
The compound represented by the following general formula (1) will be described.

In the general formula ^{(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, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Substituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted It represents a mono arylaminocarbonyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.

  The compound represented by the general formula (1) has an amino group having a specific substituent. Although the mechanism of action is unknown, it is considered that the compound represented by the general formula (1) has such a structure and exhibits high saturation, excellent printing density, light resistance, and gas resistance.

In the general formula ^{(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 represents 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 a substituent selected from the substituent group A.

In general formula (1), R ¹ , R ⁵ , R ⁶ and R ¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted, from the viewpoint of availability of raw materials and ease of synthesis. It preferably represents a substituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a carboxyl group, or a halogen atom, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted alkoxy group, and 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 still more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In general formula (1), R ⁴ and R ⁹ are each independently a hydrogen atom, substituted or non-substituted from the viewpoint of availability of raw materials and ease of synthesis, light resistance, gas resistance, print density, and saturation. Substituted 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 Alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureido group, sulfo group, carboxyl group, Or a halogen atom, 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 arylureido group Or a sulfo group, particularly preferably a hydrogen atom or a sulfo group. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In general formula (1), R ³ and R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted group, from the viewpoint of availability of raw materials and ease of synthesis. Or an unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino Preferably represents a 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, more preferably a hydrogen atom. A substituted or unsubstituted alkyl group or a sulfo group, especially Mashiku is 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 still more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In the general formula (1), R ¹¹ , R ¹⁴ , R ¹³ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom from the viewpoint of availability of raw materials and ease of synthesis. Preferably represents 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, and more A hydrogen atom, a hydroxy group, a halogen atom, or a sulfo group is preferable, and a hydrogen atom is particularly preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

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

From the viewpoint of solubility, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R in general formula (1) ^At least one of ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ preferably has an ionic hydrophilic group such as a carboxyl group, a sulfo group, or a phosphono group. Examples of counter cations of these ionic hydrophilic groups include protons, lithium ions, sodium ions, potassium ions and other alkali metal cations, ammonium ions, and the like. From the viewpoint of ease of handling as dye powders, alkali metals A cation is preferred.

In general formula (1), R ¹⁰¹ and R ¹⁰² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, Substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted It represents a substituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted alkyl group, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, a methyl group or an ethyl group. Is more preferable. Moreover, as a substituent in case an alkyl group has a substituent, the substituent chosen from the said substituent group A is mentioned, An aryl group is preferable and a phenyl group is especially preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted aryl group, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and further preferably a phenyl group. . In addition, examples of the substituent in the case where the aryl group has a substituent include a substituent selected from the above substituent group A.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted heterocyclic group, the heterocyclic group is preferably a triazine group, a thiazolyl group, a benzothiazolyl group, or a thiadiazolyl group. In addition, examples of the substituent in the case where the heterocyclic group has a substituent include a substituent selected from the above substituent group A, and a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group are preferable.
The alkylsulfonyl group in the case where R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 6 carbon atoms, more preferably an alkylsulfonyl group having 1 to 3 carbon atoms, and methyl More preferred is a sulfonyl group. In addition, examples of the substituent when the alkylsulfonyl group has a substituent include a substituent selected from the above substituent group A.
In the case where R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted arylsulfonyl group, the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 14 carbon atoms, more preferably an arylsulfonyl group having 6 to 10 carbon atoms, More preferred is a sulfonyl group. In addition, examples of the substituent in the case where the arylsulfonyl group has a substituent include a substituent selected from the above substituent group A, and a carboxyl group is particularly preferable.
In the case where R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted alkoxycarbonyl group, the alkoxycarbonyl group is preferably represented by —COOR ²⁰¹ . Here, R201 represents 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. In addition, examples of the substituent in the case where the alkoxycarbonyl group has a substituent include a substituent selected from the above substituent group A.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted aryloxycarbonyl group, the aryloxycarbonyl group is preferably represented by —COOR ²⁰² . R ²⁰² represents 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. In addition, examples of the substituent in the case where the aryloxycarbonyl group has a substituent include a substituent selected from the above substituent group A, and a nitro group is particularly preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted monoalkylaminocarbonyl group, the monoalkylaminocarbonyl group is preferably represented by —CONHR ²⁰³ . Here, R ²⁰³ represents 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, a methyl group, an ethyl group, an isopropyl group, a hexyl group. 2-ethylhexyl group, dodecyl group and cyclohexyl group are more preferable, and isopropyl group is particularly preferable. In addition, the substituent in the case where the monoalkylaminocarbonyl group has a substituent includes a substituent selected from the above substituent group A, and particularly a phenyl group, a carboxyl group, a substituted or unsubstituted amino group, and a hydroxyl group. preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted dialkylaminocarbonyl group, 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.
In addition, examples of the substituent in the case where the dialkylaminocarbonyl group has a substituent include a substituent selected from the above substituent group A, a carboxyl group, preferably an alkyloxycarbonyl group having 2 to 6 carbon atoms, and more An alkyloxycarbonyl group such as an ethyloxycarbonyl group is particularly preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted monoarylaminocarbonyl group, the monoarylaminocarbonyl group is preferably represented by —CONHR ²⁰⁶ . R ²⁰⁶ represents 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. In addition, examples of the substituent in the case where the monoarylaminocarbonyl group has a substituent include a substituent selected from the above substituent group A, and include a carboxyl group, a hydroxyl group, and a phosphono group, preferably an alkoxy having 1 to 6 carbon atoms. Group, more preferably an alkoxy group such as a cyclohexyloxy group.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted diarylaminocarbonyl group, the diarylaminocarbonyl group is preferably represented by —CONR ²⁰⁷ R ²⁰⁸ . Wherein ^{R 207} and ^{R 208} represents an aryl group having 6 to 14 carbon atoms each independently, preferably an aryl group having 6 to 10 carbon atoms, a phenyl group is more preferable. In addition, examples of the substituent in the case where the diarylaminocarbonyl group has a substituent include a substituent selected from the above substituent group A.

R ¹⁰¹ and R ¹⁰² are preferably a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted group, from the viewpoint of saturation, light resistance and gas resistance. Or an unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted monoalkylaminocarbonyl group, a substituted or unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, or A substituted or unsubstituted 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 Dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, or substituted or unsubstituted diarylaminocarbonyl group, particularly preferably substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylamino A carbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, or a substituted or unsubstituted diarylaminocarbonyl group.

Although the specific example of a compound represented by General formula (1) below is given, it is not necessarily limited to these. In the structural formulas of the following specific compounds, Me represents a methyl group, Et represents an ethyl group,
i-Pr represents an isopropyl group, and n-Bu represents an n-butyl group. Moreover, the ratio in R and M is a molar ratio.

  The first dye, which is a compound represented by the above general formula (1), has high chroma and excellent color developability particularly in a wavelength range with high lightness, and further suppresses a decrease in color development compared to conventional dyes. Tend to be excellent in gas resistance. On the other hand, the first dye tends to fade from a low concentration when exposed to a gas such as ozone gas. Therefore, by using the first dye in combination with a second dye which is difficult to fade at a low concentration, which will be described later, not only gas resistance but also excellent color developability and granularity at a low concentration. An inkjet ink composition from which an image can be obtained can be provided. That is, an image recorded using the inkjet ink composition according to the present embodiment is compared with a conventional dye ink that fades from a low density due to the complementary action of the first dye and the second dye. In addition, a light ink having a high gas resistance life can be obtained, and the discoloration balance in leaving the environment exposed to a gas such as ozone gas can be improved. Furthermore, it will be excellent in color developability and graininess.

In the compound represented by the general formula (1), it is preferable that R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ are each independently an alkyl group having 1 to 6 carbon atoms. In this case, even when used as a light magenta ink having a low dye concentration, an ink-jet ink composition is obtained which is excellent in gas resistance and further has an excellent color developability and granularity.

  In the inkjet ink composition according to this embodiment, the content of the first dye is particularly preferably included so that the maximum absorbance at 1000-fold dilution of the inkjet ink composition is 0.10 or more and 0.80 or less. It is not limited. For example, the content of the first dye is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total mass of the inkjet ink composition, and 0.4 More preferably, it is at least mass%. In the ink composition according to this embodiment, the content of the first dye is preferably 2.0% by mass or less, and 1.2% by mass or less with respect to the total mass of the ink composition. More preferably, it is 1.0% by mass or less.

  When the content of the first dye is within the above range, when the ink-jet ink composition according to this embodiment is used as a light magenta ink used together with a magenta ink, an image excellent in gas resistance can be obtained. It becomes an ink composition, and fading is suppressed in a light color region having a low recording density. Further, by using in combination with a second dye described later, it is possible to improve the gas resistance in a light color region where the recording density is low, and to improve the fading balance when left in the environment.

一般式（２）中、Ａ^Ｍ１は、炭素数１もしくは２のアルキレン基、フェニレン基を含有する炭素数１もしくは２のアルキレン基又は下記一般式（３）で表される基を表し、Ｘ^Ｍ１は、アミノ基、ヒドロキシ基、塩素原子、又はスルホ基もしくはカルボキシ基で置換されたフェノキシ基を表す。

一般式（３）中、Ｒ^Ｍ１は、水素原子又はアルキル基を表す。 1.2. Second Dye The inkjet ink composition according to the present embodiment includes a second dye that is a compound represented by the following general formula (2) as a dye. The dye represented by the general formula (2) may form a salt.

In General Formula (2), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following general formula (3), and X ^M1 Represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.

In General Formula (3), R ^M1 represents a hydrogen atom or an alkyl group.

In the general formula (2), A ^M1 is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.

In General Formula (2), X ^M1 represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group. Among these, a phenoxy group substituted with a sulfo group or a carboxy group is preferable, and a phenoxy group substituted with a carboxy group is more preferable. A phenoxy group substituted with a carboxy group has a favorable effect of improving gas resistance, and a phenoxy group substituted with two carboxy groups is particularly preferable because it has better gas resistance.

  In the general formula (2), specific examples of the phenoxy group substituted with a sulfo group or a carboxy group include 4-sulfophenoxy, 2,4-disulfophenoxy, 4-carboxyphenoxy, and 3,5-dicarboxyphenoxy. More preferably 4-carboxyphenoxy and 3,5-dicarboxyphenoxy, and still more preferably 3,5-dicarboxyphenoxy.

  Examples of the salt of the compound represented by the general formula (2) include ammonium salts and alkali metal salts.

  The second dye, which is a compound represented by the above general formula (2), has a color property and gas resistance which are inferior to those of the first dye, but has excellent particle characteristics. On the other hand, the second dye tends to fade from a high concentration when exposed to a gas such as ozone gas. Therefore, by using the second dye in combination with the first dye, fading occurs simultaneously at all densities when fading, so that it is possible to balance the fading of the entire image. Therefore, the complementary action of both dyes provides a light ink having a higher gas resistance life than conventional dye inks that fade from a low density. Furthermore, it will be excellent in color developability and graininess.

In the inkjet ink composition according to this embodiment, the second dye is preferably a compound represented by the following general formula (4).

  In the case where the second dye is a compound represented by the above general formula (4), the ink is further excellent in gas resistance even when used at a low concentration.

In the inkjet ink composition according to the present embodiment, the content of the second dye is particularly preferably included so that the maximum absorbance at 1000-fold dilution of the inkjet ink composition is 0.10 or more and 0.80 or less. It is not limited. The content of the second dye is, for example, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on the total mass of the inkjet ink composition, and 0.4 More preferably, it is at least mass%. In the ink composition according to this embodiment, the content of the second dye is preferably 2.0% by mass or less, and 1.2% by mass or less with respect to the total mass of the ink composition. More preferably, it is 1.0% by mass or less.

  When the content of the second dye is within the above range, when the ink-jet ink composition according to this embodiment is used as a light ink, fading in a light color region with a low recording density is suppressed. Further, by using it together with the first dye described above, it is possible to improve the gas resistance in a light color region where the recording density is low and to improve the fading balance when left in the environment.

1.3. Water-soluble organic solvent The ink-jet ink composition according to this embodiment may contain a water-soluble organic solvent. Although it does not specifically limit as a water-soluble organic solvent, A volatile water-soluble organic solvent is used preferably.

  Examples of the water-soluble organic solvent include alkylbetaine, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,2-pentanediol. 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono- iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monobuty Ether, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Butylme Ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dimethyl ether, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, alcohols or glycols such as tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl 2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl 2-imidazolidinone, dimethyl sulfoxide, sulfur Examples include holan and 1,1,3,3-tetramethylurea.

  Said water-soluble organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the water-soluble organic solvent is not particularly limited and can be appropriately determined as necessary. For example, when the ink has excellent permeability, moisture retention, and ejection stability to the recording medium, it is preferable to use alkylbetaine, glycerin, triethylene glycol, triethylene glycol monobutyl ether, or triethanolamine. .

  The addition amount of the organic solvent is preferably 5% by mass or more and 25% by mass or less, more preferably 7.5% by mass or more and 22% by mass or less, and more preferably 10% by mass or more and 20% by mass or less with respect to the total amount of the ink. More preferably, it is at most mass%.

  Among these, the water-soluble organic solvent preferably contains triethylene glycol monobutyl ether, and the content of triethylene glycol monobutyl ether is preferably 2.0% by mass or more and 15% by mass or less. It is more preferably from 1% by mass to 12.5% by mass, and further preferably from 3% by mass to 10% by mass. When the addition amount of triethylene glycol monobutyl ether is within the above range, ejection stability is improved.

1.4. Surfactant The inkjet ink composition according to this embodiment preferably contains a surfactant. When the inkjet ink composition according to the present embodiment contains a surfactant, the dynamic surface tension and wettability of the ink can be adjusted, and the ejection stability can be improved.

  The surfactant is not particularly limited, but is an acetylene glycol surfactant, a fluorine surfactant, and a silicone interface in terms of adjusting the dynamic surface tension and wettability of the ink and improving ejection stability. An activator is mentioned.

The acetylene glycol surfactant is not particularly limited, but is an acetylene glycol surfactant having an HLB value of 4 or less, an alkylene oxide adduct of acetylene glycol having a main chain carbon number of 12 or more, and the main chain carbon number. It is preferable to use an acetylene glycol-based surfactant such as acetylene glycol having 10 or more. Here, the HLB (Hydrophile-Lipophile Balance) value of the surfactant is a value calculated by the Griffin method. Specifically, the HLB value of the surfactant can be calculated according to the following formula (H).
HLB value = 20 × (mass% of hydrophilic group) (H)

  Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7. Alkylene oxide adducts of diols, alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol, 2,5,8,11-tetra Examples include ethoxylates of methyl-6-dodecine-5,8-diol and ethoxylates of 5,8-dimethyl-6-dodecine-5,8-diol. Among the alkylene oxide adducts of acetylene glycol, an ethylene oxide adduct of acetylene glycol and a propylene oxide adduct of acetylene glycol are preferable, and an ethylene oxide adduct of acetylene glycol is more preferable.

  Although it does not specifically limit as a commercial item of an acetylene glycol type surfactant, For example, Olphine 104 series, E series (or more) of Olphine E1010, Orphine EXP4300 (carbon number 12-ethylene oxide addition product), Surfynol 61, Surfy 465, Surfynol 104S (HLB4), Surfinol 104PG50 (HLB4, 2,4,7,9-tetramethyl-5-decyne-4,7-diol), Surfynol 420 (HLB4), Surfynol 82 (HLB4) ), Surfynol DF110D (HLB3, 2,5,8,11-tetramethyl-6-dodecine-5,8-diol), Surfynol MD-20 (HLB4), etc. (trade name, manufactured by Air Products Japan Co., Ltd.) Is mentioned. These surfactants may be used alone or in combination of two or more.

The fluorosurfactant is not particularly limited. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkyl betaine, A fluoroalkylamine oxide compound is mentioned. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, S-144, S-145 (brand name, Asahi Glass Co., Ltd. product); FC-170C, FC-430, Fluorard-FC4430 (brand name, Sumitomo 3M Limited); FSO, FSO-100, FSN, FSN-100, FS-300 (trade name, manufactured by Dupont); FT-250, 251 (trade name, manufactured by Neos Co., Ltd.), and the like. A fluorine-type surfactant may be used individually by 1 type, and may use 2 or more types together.

  Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Although it does not specifically limit as a commercial item of a silicone type surfactant, Specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349 (trade name, manufactured by Big Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, Examples thereof include KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  The content of the surfactant is preferably 0.1% by mass or more and 1.5% by mass or less, and preferably 0.2% by mass or more and 1.2% by mass or less with respect to the total mass of the ink composition. Is more preferable, and it is further more preferable that it is 0.3 mass% or more and 1.0 mass% or less. When the content of the surfactant is within the above range, the ejection stability is further improved.

1.5. Water The inkjet ink composition according to this embodiment may further contain water.

  Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the ink is stored for a long period of time. Thereby, storage stability improves more.

  The water content is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more with respect to the total mass of the inkjet ink composition. When the water content is within the above range, the ejection characteristics and image quality are further improved.

1.6. pH adjuster The inkjet ink composition according to the present embodiment may contain a pH adjuster. The pH adjuster can easily adjust the pH value of the ink. The pH adjuster is not particularly limited. For example, inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia, triethanolamine, diethanolamine and monoethanolamine Organic bases such as tripropanolamine, and organic acids such as adipic acid, citric acid, and succinic acid. A pH adjuster may be used individually by 1 type, and may be used in mixture of 2 or more types.

1.7. Other Components The ink-jet ink composition according to the present embodiment is a dissolution aid for maintaining good storage stability and ejection stability from the head, for improving clogging, or for preventing ink deterioration. Add various additives such as viscosity modifiers, pH modifiers, antioxidants, preservatives, antifungal agents, corrosion inhibitors, and chelating agents to capture metal ions that affect dispersion You can also

1.8. Method for Preparing Inkjet Ink Composition The inkjet ink composition according to the present embodiment is obtained by mixing the components described above in an arbitrary order, and removing impurities by filtering or the like as necessary. As a method for mixing the components, a method in which materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is suitably used. As a filtration method, centrifugal filtration, filter filtration, or the like can be performed as necessary.

1.9. Physical Properties of Inkjet Ink Composition The inkjet ink composition according to this embodiment has a surface tension at 20 ° C. of 20 mN / m or more and 50 mN / m from the viewpoint of the balance between recording quality and reliability as an inkjet ink. It is more preferable that it is 25 mN / m or more and 40 mN / m or less. For surface tension measurement, use an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) to check the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. Can be measured.

  From the same viewpoint, the viscosity at 20 ° C. of the inkjet ink composition according to this embodiment is preferably 1 mPa · s to 8 mPa · s, and more preferably 2 mPa · s to 6 mPa · s. preferable. The viscosity can be measured using a vibration viscometer VM-100AL (trade name, manufactured by Yamaichi Electronics Co., Ltd.).

1.10. Applications The ink-jet ink composition according to this embodiment is stored in an ink cartridge of a known ink-jet recording apparatus, ejects ink droplets, and attaches the droplets to a recording medium such as paper to record an image. Can do. The ink jet recording apparatus is preferably an ink jet recording apparatus that is equipped with an electrostrictive element that can vibrate based on an electrical signal and that can eject ink by the vibration of the electrostrictive element. Although it does not specifically limit as a recording medium, For example, paper, cardboard, a textile product, leather, a sheet | seat or film, a plastics, glass, ceramics, a metal etc. are mentioned.

  In general, adding light ink to an ink set is known to improve the graininess of an image. In particular, light color areas in which light ink is used have a low recording density and fading in light color areas. It tends to be faster than the intermediate color area which is a high density recording area. For this reason, among ink sets containing conventional light ink, in particular, ink sets containing light magenta ink have found a new problem that the gray balance is liable to be lost due to ozone and other gases when left in the environment and the color fading balance is lowered. .

  The ink-jet ink composition according to the present embodiment uses the first dye and the second dye as the dye, so that the complementary action of the first dye and the second dye can reduce the conventional low concentration. A light magenta ink having a higher gas resistance life than a dye ink that fades is obtained. This suppresses fading in light color areas where the recording density using light magenta ink is low, and in recording using the ink-jet ink composition according to this embodiment together with magenta ink, the fading speed is the same in all areas. Thus, the fading balance between the light color area where the light magenta ink is used and the area recorded using the other ink can be improved. Furthermore, it will be excellent in color developability and graininess.

2. Ink Set The inkjet ink composition according to this embodiment can be used as an ink set containing light magenta ink and magenta ink. In this case, the ink composition having a higher dye content on a mass basis is the magenta ink that is the dark ink composition, and the ink composition having a lower dye content on the mass basis than the dark ink composition is the light ink composition. A light magenta ink is used.

In the ink set according to the present embodiment, the light magenta ink and the magenta ink are the same color inks. The “same color system” means “having substantially the same hue angle”, and the hue angle of each recorded image recorded on the white recording medium by the light ink composition and the dark ink composition. It means that the difference in H ° is within 30 °. Here, the hue angle ∠H ° is defined in the CIELAB color space, and ∠H ° = tan ⁻¹ (b ^* / a ^* ) + 180 (when a ^* <0), or ∠H ° = tan ⁻¹ ( b ^* / a ^* ) + 360 (when a ^* > 0).

Here, a ^* and b ^* represent the perceptual chromaticity index defined in the CIELAB color space. Therefore, the light magenta ink and the magenta ink each containing only the same dye can be regarded as the same color ink.

  The ink set according to the present embodiment can be suitably used as an ink set of cyan ink and yellow ink in addition to light magenta ink and magenta ink, and may further include other inks.

  The ink set according to the present embodiment is housed in an ink cartridge of a known ink jet recording apparatus, and ejects ink droplets in the same manner as the ink jet ink composition according to the present embodiment, and is applied to a recording medium such as paper. An image can be recorded by depositing droplets. The ink jet recording apparatus is preferably an ink jet recording apparatus that is equipped with an electrostrictive element that can vibrate based on an electrical signal and that can eject ink by the vibration of the electrostrictive element. Although it does not specifically limit as a recording medium, For example, paper, cardboard, a textile product, leather, a sheet | seat or film, a plastics, glass, ceramics, a metal etc. are mentioned.

  In the ink set according to the present embodiment, the light magenta ink includes the ink-jet ink composition according to the present embodiment, and the recording is performed using the ink set, whereby a light color region using the light magenta ink has a low recording density. Fading is suppressed, and the speed of fading in all areas is the same. As a result, in the ink set according to the present embodiment, the fading balance between the light color area where the light ink is used and the area recorded using the other ink is improved.

3. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

3.1. Preparation of Ink Composition Each component was mixed and stirred at the blending amounts shown in Table 1, and subjected to pressure filtration with a membrane filter having a pore diameter of 10 μm to obtain each ink composition. The numerical values in Table 1 represent the content (% by mass) in the ink, and water was added so that the total mass of the ink composition was 100% by mass.

  Among the components used in Table 1, Surfinol 104PG50 is an acetylene glycol surfactant made of Air Products Japan Co., Ltd., having 10 main chain carbon atoms without an alkylene oxide adduct.

Of the components used in Table 1, the dyes are as follows.
Magenta dye 1: the above exemplified compound (1-20)
-Magenta dye 2: The above exemplified compound (4)
-Magenta dye 3: The following exemplary compound (M-3)

In addition, exemplary compound (1-20) is paragraph number 013 of Unexamined-Japanese-Patent No. 2016-41801.
The compound was synthesized as follows with reference to the method described in No. 6-0155.

<Synthesis of Exemplary Compound (1-20)>

<Synthesis of Intermediate (B)>
23.0 g of the intermediate (A) (synthesized by the method described in paragraph No. 0065 on page 17 of JP 2011-148873 A) was added to 420 g of 10% fuming sulfuric acid and reacted at room temperature for 48 hours. . The reaction solution was poured into a large excess of ethyl acetate, and the precipitated crystals were filtered off. The crystals separated by filtration were dissolved in 500 mL of methanol, adjusted to pH 7 using a 28% sodium methoxide methanol solution, and the precipitated sodium sulfate was removed by filtration. The filtrate was concentrated using a rotary evaporator, and the resulting residue was purified by column chromatography (filler: Sephadex LH-20 (trade name, manufactured by Pharmacia), developing solvent: methanol) to obtain an intermediate (B). Crystals were obtained. Yield 21.0 g, 68% yield, MS (m / z) = 793 ([M-2Na + H] ⁻ , 100%).

After adding 2.0 g of methanesulfonyl chloride to 4 g of the obtained intermediate (B), 8 mL of pyridine was slowly added dropwise and reacted at room temperature for 3 hours. The reaction solution was added to a large excess of ethyl acetate, and the precipitated crystals were separated by filtration. The obtained crystals are dissolved in 50 mL of water, adjusted to pH 7 with dilute aqueous sodium hydroxide, and the obtained aqueous solution is purified by column chromatography (filler: Sephadex LH-20, developing solvent: water / methanol), A green glossy crystal of Exemplified Compound (1-20) was obtained. Yield 3.0 g, 63% yield. MS (m / z) = 993 ([M-1] ^- , 100%). The maximum absorption wavelength of the absorption spectrum of Exemplified Compound (1-20) in a dilute aqueous solution was 533 nm, and the molar extinction coefficient was 54000.

  Exemplified compounds (4) and (M-3) were synthesized with reference to the method described in JP-A-2016-29149.

3.2. Evaluation test for ink composition 3.2.1. Evaluation of color development (ABS measurement)
Each ink was diluted 1000 times with ultrapure water, and the maximum absorbance of the maximum peak of the UV-visible absorption spectrum was measured using an UV-visible spectrophotometer under the following conditions. In the ultraviolet-visible absorption spectrum obtained by measuring with an ultraviolet-visible spectrophotometer, the “maximum peak” means the peak when it has only one peak (maximum value) in the measured wavelength range, In the case of having a plurality of peaks, it means the peak having the highest peak apex absorbance (ABS) among the plurality of peaks.

Apparatus: UV-visible spectrophotometer V-770 series (manufactured by JASCO Corporation)
Parameter file Metering mode: ABS
Measurement range: 800-300nm
Data capture interval: 0.5 nm
UV / Vis bandwidth: 2.0 nm
NIR bandwidth: 8.0 nm
UV / Vis response: 0.06 sec
NIR response: 0.06 sec
Scanning speed: 400 nm / min
Light source switching: 340nm
Diffraction grating switching: 850 nm
Light source: D2 / WI
Filter switching: Step Correction: Baseline

3.2.2. Evaluation of ozone resistance (measurement of ROD value)
After filling the ink container of the following evaluation machine with ink, the change from the initial value of the OD (Optical Density) value in the area where each ink was solid-printed under the following conditions was measured, and ozone resistance was measured according to the following evaluation criteria. Evaluated. Note that the OD change at the 16th gradation in the 16 gradations and the 1st gradation among the 16 gradations in the dark color determination is the relative optical density ROD (Relativistic) from the initial stage.
Judged by Optical Density).
(Test conditions)
Evaluation machine: Trade name “EP-808AW”, manufactured by Seiko Epson Corporation Recording medium: manufactured by Seiko Epson Corporation, photo paper <glossy>, no color correction Print resolution: 1440 dpi × 720 dpi
Exposure conditions: 23 ° C, relative humidity 50%, ozone concentration 5 ppm
Measurement conditions: Colorimeter X-Rite i1 (trade name, X-Rite),
No light source filter, light source: D50, viewing angle 2 degrees Sample patch: prints 16 gradations for each color,
(Evaluation criteria)
A: ROD does not decrease to 70% by 40 hours exposure time.
B: ROD decreases to 70% over 24 hours and 40 hours or less.
C: ROD decreases to 70% in less than 24 hours.

3.3. Evaluation Results for Ink Composition In the examples containing both the magenta dye 1 and the magenta dye 2, the evaluation of ozone resistance of dark and light colors was A or B, and the ozone resistance was excellent. In particular, the higher the magenta dye 1 content, the better the ozone resistance of the dark color. In Example 1 in which the content of both the magenta dye 1 and the magenta dye 2 was 0.60%, Both the light-colored ozone resistance evaluations were A.

On the other hand, in Comparative Example 1 containing only the magenta dye 1, the light-colored ozone resistance evaluation was C. On the other hand, in Comparative Example 2 including only the magenta dye 2, the evaluation of dark ozone resistance was C. As shown in Example 5, when magenta dye 2 was added to Comparative Example 1 so that the content was 0.1%, the light-colored ozone resistance evaluation was improved to B. Further, as shown in Example 4, when magenta dye 1 was added to Comparative Example 2 so that the content was 0.1%, the evaluation of dark ozone resistance was improved to B. As described above, the inclusion of both the magenta dye 1 and the magenta dye 2 improved the evaluation of ozone resistance of dark and light colors, and improved the fading balance when left in an environment exposed to ozone gas.

  In Comparative Example 3 containing only the magenta dye 3 alone, the evaluation of ozone resistance of dark and light colors was C. In Comparative Example 4 containing magenta dye 2 and magenta dye 3, the evaluation was reversed from that in Comparative Example 2. In Comparative Example 5 containing magenta dye 1 and magenta dye 3, the evaluation was the same as in Comparative Example 1. Thus, even when the magenta dye 1 and the magenta dye 2 are combined with the magenta dye 3, the fading balance is not improved.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (6)

A first dye that is a compound represented by the following general formula (1) and a second dye that is a compound represented by the following general formula (2), and the maximum absorbance at 1000-fold dilution is 0. The inkjet ink composition which is 10 or more and 0.80 or less.

In the general formula ^{(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, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Substituted heterocyclic group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted carbamoyl group Substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted It represents a mono arylaminocarbonyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted alkyl aryl amino carbonyl group.

In the general formula (2), A ^M1 represents an alkylene group having 1 or 2 carbon atoms, an alkylene group having 1 or 2 carbon atoms containing a phenylene group, or a group represented by the following general formula (3), and X ^M1 Represents an amino group, a hydroxy group, a chlorine atom, or a phenoxy group substituted with a sulfo group or a carboxy group.

In General Formula (3), R ^M1 represents a hydrogen atom or an alkyl group. The inkjet ink composition according to claim 1, wherein the second dye is a compound represented by the following general formula (4).

  The content of the dye that is the compound represented by the general formula (1) is 0.1% by mass or more and 1.2% by mass or less with respect to the total mass of the ink composition. The ink-jet ink composition described in 1. In the compound represented by the general formula (1), the R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ each independently represents an alkyl group having 1 to 6 carbon atoms. The inkjet ink composition according to any one of claims 3 to 4.   The inkjet ink composition according to any one of claims 1 to 4, which is a light magenta ink used together with a magenta ink. An ink set including light magenta ink and magenta ink,
An ink set, wherein the light magenta ink is the inkjet ink composition according to any one of claims 1 to 5.