JP6988616B2 - Ink set and inkjet recording method - Google Patents

Description

The present invention relates to an ink set and an inkjet recording method.

In the inkjet recording method, high-definition images can be recorded by supplying ink to the print head, ejecting small droplets of ink from the print head and adhering them on a recording medium such as paper, and rapidly in each direction. Has made great progress. Among them, various studies have been made on the improvement of the obtained image.

For example, Patent Document 1 discloses a technique for improving color development, gas resistance, and light resistance in an ink set composed of cyan, magenta, and yellow ink, which are basic colors.

Japanese Unexamined Patent Publication No. 2017-171753

However, in the above, the robustness of the monochrome image (hereinafter, also referred to as “composite gray”) is insufficient, and the heat resistance and moisture resistance are particularly insufficient.

一般式（１）中、
破線で表される環Ａ乃至Ｄ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又は６員環の含窒素複素芳香環を表し、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り、
ＥはＣ２−Ｃ１２アルキレンを表し、
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、Ｃ１−Ｃ６アルコキシ基、アミノ基、モノＣ１−Ｃ４アルキルアミノ基、ジＣ１−Ｃ４アルキルアミノ基、モノＣ６−Ｃ１０アリールアミノ基、ジＣ６−Ｃ１０アリールアミノ基、Ｃ１−Ｃ３アルキルカルボニルアミノ基、ウレイド基、Ｃ１−Ｃ６アルキル基、ニトロ基、シアノ基、ハロゲン原子、Ｃ１−Ｃ６アルキルスルホニル基、及びＣ１−Ｃ６アルキルチオ基よりなる群から選択される１種類又は２種類以上の置換基を有しても良い、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又はホスホノナフチルアミノ基であり、
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；Ｃ１−Ｃ６アルコキシ基；アミノ基；モノＣ１−Ｃ６アルキルアミノ基；ジＣ１−Ｃ６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；Ｃ１−Ｃ３アルキルカルボニルアミノ基；ウレイド基；Ｃ１−Ｃ６アルキル基；ニトロ基；シアノ基；ハロゲン原子；Ｃ１−Ｃ６アルキルスルホニル基；又はアルキルチオ基；を表し、
基Ｆはフェニレン基；又は、６員含窒素複素芳香環基；を表し、
ａは１以上６以下の整数を表し、
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、
且つｂ及びｃの和は、平均値で１．００以上４．００未満である。 [Application Example 1]
One aspect of the ink set according to the present invention is
An ink set containing cyan ink, magenta ink, and yellow ink.
The cyan ink contains a porphyrazine-based compound represented by the following general formula (1) or a salt thereof.
The magenta ink contains a compound having a xanthene skeleton or a salt thereof,
The yellow ink contains a compound having a dimeric disazo structure formed by binding via a triazine skeleton or a salt thereof.

In general formula (1),
The rings A to D represented by the broken lines represent benzene rings or 6-membered nitrogen-containing heteroaromatic rings independently fused to porphyrazine rings, and the number of nitrogen-containing heteroaromatic rings is 0.00 on average. More than 3.00 or less, the rest are benzene rings,
E represents C2-C12 alkylene and represents
X has a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group and a di-C1-C4 alkylamino group as substituents. , Mono C6-C10 arylamino group, diC6-C10 arylamino group, C1-C3 alkylcarbonylamino group, ureido group, C1-C6 alkyl group, nitro group, cyano group, halogen atom, C1-C6 alkylsulfonyl group, And may have one or more substituents selected from the group consisting of C1-C6 alkylthio groups, sulfoanilino groups, carboxyanilino groups, phosphonoanilino groups, sulfonaphthylamino groups, carboxynaphthylamino groups or It is a phosphononaphthylamino group and
R is a hydrogen atom; a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono C1-C6 alkylamino group; a diC1-C6 alkylamino group; a mono Represents an arylamino group; a diarylamino group; a C1-C3 alkylcarbonylamino group; a ureido group; a C1-C6 alkyl group; a nitro group; a cyano group; a halogen atom; a C1-C6 alkylsulfonyl group; or an alkylthio group;
Group F is phenylene group; or 6-membered nitrogen-containing heteroaromatic ring group; represent,
a represents an integer of 1 or more and 6 or less,
b has an average value of 0.00 or more and less than 3.90.
c has an average value of 0.10 or more and less than 4.00.
Moreover, the sum of b and c is 1.00 or more and less than 4.00 on average.

[Application example 2]
In application example 1,
In the porphyrazine-based compound represented by the general formula (1) or a salt thereof,
The nitrogen-containing heteroaromatic rings in the rings A to D are independently fused pyridine rings at the 2- and 3-positions or at the 3- and 4-positions; or pyrazine rings condensed at the 2- and 3-positions. ,
E is a linear C2-C4 alkylene,
X is a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group, a diC1-C4 alkylamino group, a C1-C3 alkylcarbonylamino group, and a nitro as substituents. It may have 0 to 2 substituents of 1 or 2 selected from the group consisting of groups, halogen atoms, C1-C6 alkylsulfonyl groups and alkylthio groups; sulfoanilino groups; sulfo groups as substituents. , A carboxyanilino group which may have 0 to 2 substituents of 1 or 2 selected from the group consisting of a carboxy group, a hydroxy group, and a sulfamoyl group; a phosphonoanilino group; or a sulfo as a substituent. A sulfonaphthylamino group which may have 0 to 2 substituents of one or two types selected from a group and a hydroxy group;
R is a hydrogen atom; a sulfo group; a carboxy group; a C1-C6 alkoxy group; a C1-C6 alkyl group; or a halogen atom;
Group F is phenylene group; Or, R is pyridyl group is a hydrogen atom; a,
a can be an integer of 1 or 2.

[Application example 3]
In application example 1 or application example 2,
In the porphyrazine-based compound represented by the general formula (1) or a salt thereof,
The nitrogen-containing heteroaromatic rings in the rings A to D are pyridine rings that are independently fused at the 2- and 3-positions, respectively.
E is ethylene,
X is a sulfoanilino group which may have 0 or 1 sulfo group as a substituent; or a sulfonaphthylamino group which has 2 sulfo groups as a substituent.
R is a hydrogen atom, a sulfo group, or a carboxy group,
Group F is phenylene group, or a pyridyl group R is a hydrogen atom,
a is an integer of 1
b is 0.00 or more and less than 3.90 on average,
c is an average value of 0.10 or more and less than 4.00,
Moreover, the sum of b and c can be 1.00 or more and less than 4.00 on average.

一般式（２）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。 [Application example 4]
In any one of Application Example 1 to Application Example 3
The compound having a xanthene skeleton can be a compound represented by the following general formula (2).

In the general formula (2), 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 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or absent, respectively. Substituent 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 , Substituent or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, or substituted or unsubstituted alkyl Represents an arylaminocarbonyl group.

[Application Example 5]
In application example 4,
In the compound represented by the general formula (2), the R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ can each independently represent an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms.

一般式（３）中、
Ｍは、水素原子、金属元素、金属酸化物、金属水酸化物、または金属ハロゲン化物を表し、
Ｚ_１〜Ｚ_４は、それぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アラルキル基、アリール基、またはヘテロ環基を表し、各々はさらに置換基を有してもよい。 [Application example 6]
In any one of Application Example 1 to Application Example 5
Further, the cyan ink can contain a phthalocyanine compound represented by the following general formula (3).

In general formula (3),
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
Z ₁ to Z ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, each may further have a substituent.

一般式（３−１）中、ＲはＳＯ_２（ＣＨ_２）_３ＳＯ_３Ｎａを表す。

一般式（３−２）中、Ｒのいずれか２つはＳＯ_２（ＣＨ_２）_３ＳＯ_３Ｌｉを表し、残りの２つはＳＯ_２（ＣＨ_２）_３ＳＯ_２ＮＨＣＨ_２ ＣＨ（ＯＨ）ＣＨ_３を表す。 [Application 7]
In application example 6,
The compound represented by the general formula (3) can contain a compound represented by the following general formula (3-1) and a compound represented by the following general formula (3-2).

In the general formula (3-1), R represents SO ₂ (CH ₂ ) ₃ SO ₃ Na.

In the general formula (3-2), any two of R represent SO ₂ (CH ₂ ) ₃ SO ₃ Li, and the remaining two represent SO ₂ (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH. Represents _3.

[Application Example 8]
In any one of application examples 1 to 7,
Further, the magenta ink can contain a compound represented by the following general formula (4).

[Application 9]
One aspect of the inkjet recording method according to the present invention is
It is an inkjet recording method in which ink is ejected by an inkjet method and an image is recorded on a recording medium.
The ink is cyan ink, magenta ink, and yellow ink constituting the ink set according to any one of Application Examples 1 to 8.

Hereinafter, preferred embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described. The embodiments described below describe an example of the present invention. Further, the present invention is not limited to the following embodiments, and includes various modifications implemented without changing the gist of the present invention. Not all of the configurations described below are essential configurations of the present invention.

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

1. 1. Ink set The ink set according to the embodiment of the present invention is an ink set containing cyan ink, magenta ink and yellow ink, and the cyan ink is a porphyrazine compound represented by the above general formula (1) or a porphyrazine-based compound. A compound having a dimer dysazo structure or a salt thereof, which contains the salt and the magenta ink contains a compound having a xanthene skeleton or a salt thereof, and the yellow ink is bonded via a triazine skeleton. It is characterized by containing.

Hereinafter, the components contained in the cyan ink, magenta ink, and yellow ink constituting the ink set according to the present embodiment, and the components that may be contained will be described.

1.1. Cyan ink 1.1.1. Porphyrazine-based compound represented by the general formula (1) The cyan ink constituting the ink set according to the present embodiment contains the porphyrazine-based compound represented by the following general formula (1) or a salt thereof.

That is, tetrabenzoporphyrazine is usually called phthalocyanine, and the four benzo (benzene) rings of more than 0 and 3 or less are replaced with nitrogen-containing heteroaromatic rings. In addition, in this specification, for convenience, both "porphyrazine-based compound or a salt thereof" are included and hereinafter abbreviated as "porphyrazine-based compound".

In the formula (1), the nitrogen-containing heteroaromatic ring in the four rings A, B, C and D represented by the broken line includes, for example, a nitrogen atom such as a pyridine ring, a pyrazine ring, a pyrimidine ring and a pyridazine ring. A nitrogen-containing heteroaromatic ring containing 1 or 2 of these can be mentioned. Among these, a pyridine ring or a pyrazine ring is preferable, and a pyridine ring is more preferable. As the number of nitrogen-containing complex aromatic rings increases, gas resistance improves, but bronze properties tend to occur more easily, and the number of nitrogen-containing complex aromatic rings tends to be appropriate while considering gas resistance and bronze properties. Adjust and select a well-balanced ratio.

The number of nitrogen-containing heteroaromatic rings cannot be unequivocally determined because it depends on the type of heterocycle, but the average value is usually more than 0.00 and 3.00 or less, preferably 0.20 or more and 2.00 or less. It is more preferably 0.50 or more and 1.75 or less, and further preferably 0.75 or more and 1.50 or less.

The remaining rings A to D are benzene rings, and similarly, the benzene rings in the rings A to P have a normal average value of 1.00 or more and less than 4.00, preferably 2.00 or more and 3.80 or less. It is preferably 2.25 or more and 3.50 or less, and more preferably 2.50 or more and 3.25 or less. In the present invention, the porphyrazine-based compound is a mixture of a plurality of compounds, as is clear from the fact that the number of nitrogen-containing heteroaromatic rings of rings A to D is represented by an average value.

Further, in the present specification, unless otherwise specified, the number of nitrogen-containing heteroaromatic rings is described up to the second decimal place by rounding off the third decimal place. However, for example, when the number of nitrogen-containing heteroaromatic rings or the number is 1.375 and the number of benzene rings is 2.625, when both are rounded off, the former becomes 1.38 and the latter becomes 2.63, and the total of both is rings A to 2. It exceeds 4.00, which is the total of D.

In such a case, for convenience, the third digit after the decimal point on the nitrogen-containing complex fragrance Korean side is truncated and only the benzene ring side is rounded off, so that the former is described as 1.37 and the latter as 2.63. As for b and C in the formula (1), as described later, in principle, the third decimal place is rounded off and the second digit is described, but in the same case, the third decimal place on the b side is described. The digits are rounded down and only the C side is rounded off.

In the above formula (1), examples of the alkylene in E include a straight chain, a branched chain or a cyclic alkylene, and a straight chain or a cyclic is preferable, and a straight chain is more preferable. The range of carbon atoms is usually C2-C12, preferably C2-C6, more preferably C2-C4, and even more preferably C2-C3.

Specific examples include linear ones such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene; branched chains such as 2-methylethylene; cyclopropylene diyl, 1 , 2- or 1,3-cyclopentylene yl, 1,2-, 1,3- or 1,4- and the like, cyclic ones such as each cyclohexylene diyl; and the like. Ethylene, propylene, butylene, pentylene, or hexylene is preferred, more preferably ethylene, propylene, or butylene, still more preferably ethylene or propylene, and particularly preferably ethylene.

In the formula (1), X represents a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group or a phosphononaphthylamino group. The number of substitutions of sulfo, carboxy and phosphono in these anilino groups and naphthylamino groups is one.

Specific examples include sulfoanilino groups such as 2-sulfoanilino, 3-sulfoanilino and 4-sulfoanilino; carboxyanilino groups such as 2-carboxyanilino, 3-carboxyanilino and 4-carboxyanilino; 2-phosphonoanilino and 3-phosphonoanilino. , 4-Phonoanoanilino groups; 3-sulfo1-naphthylamino, 6-sulfo-1-naphthylamino, 8-sulfo-1-naphthylamino, 1-sulfo-2-naphthylamino, 3-sulfo-2-naphthyl Sulfonates such as amino, 4-sulfo-2-naphthylamino, 5-sulfo-2-naphthylamino, 6-sulfo-2-naphthylamino, 7-sulfo-2-naphthylamino, 8-sulfo-2-naphthylamino, etc. Naftylamino group; etc. In addition, "phosphono" tastes a phosphate group [-P (0) (OH) _2].

As the X, a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, or a sulfonaphthylamino group is preferable, and a sulfoanilino group is particularly preferable.

The sulfoanilino group, carboxyanilino group, phosphonoanilino group, sulfonaphthylamino-group, carboxynaphthylamino-group or phosphononaphthylamino-group in X may be a sulfo group; a carboxy group; a phosphoric acid group; a sulfamoyl group as substituents. Carbamoyl group; hydroxy group; C1-C6 alkoxy group; amino-group; mono-C1-C4 alkylamino-group; di-C1-C4 alkylamino-group; monoarylamino-group; diarylamino-group; C1-C3 alkyl One or more selected from the group consisting of a carbonylamino-group; a ureido group; a C1-C6 alkyl group; a nitro group; a cyano group; a halogen atom; a C1-C6 alkylsulfonyl group; and a C1-C6 alkylthio group; It also has a group of. The group of 20 groups from the sulfo group to the C1-C6 alkylthio leather mentioned here is hereinafter abbreviated as "a group of 20 substituents" in the present specification. The number of substitutions in X of the group selected from the group of 20 substituents is usually 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. .. The substitution position of the group selected from the group of 20 substituents is not particularly limited, but the carbon atom in the anilino group and the naphthylamino-group, that is, the former is on the benzene ring, and the latter is on the naphthalene ring. It is preferred to replace it above.

Examples of the C1-C6 alkoxy group in the group of the 20 substituents include a linear, branched or cyclic group, preferably a straight chain or a branched chain, and more preferably a straight chain. The range of carbon atoms is usually C1-C6, preferably C1-C4, and more preferably C1-C3.

Specific examples are linear ones such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy; to isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isopentyroxy, iso. Branched chains such as xyloxy; cyclic ones such as cyclopropoxy, cyclopentoxy, and cyclohexyloxy; and the like can be mentioned. Of these, methoxy or ethoxy is preferable, and methoxy is particularly preferable.

Examples of the mono-C1-C4 alkylamino group in the group of 20 substituents include those having a linear or branched chain, and the range of the carbon number thereof is usually C1-C4, preferably C1-C3. Specific examples include linear ones such as methylamino, ethylamino, n-propylamino and n-butylamino; branched chains such as isopropylamino, isobutylamino, sec-butylamino and t-butylamino; and the like. Be done. Of these, methylamino is preferred.

Examples of the diC1-C4 alkylamino-group in the group of 20 substituents include a dialkylamino group having two independently of the alkyl moieties mentioned in the monoalkylamino group. Specific examples include dimethylamino, diethylamino, methylethylamino and the like. Of these, dimethylamino is preferred.

Examples of the monoarylamino group in the group of the 20 substituents include a monoC6-C10 aromatic amino group, preferably a phenylamino group or a naphthylamino group, and more preferably a phenylamino group.

Examples of the diarylamino group in the group of the 20 substituents include a diarylamino group having two independently of the aryls mentioned in the monoarylamino group. Preferred are those having the same aryl, more preferably two phenyls, and specific examples thereof include diphenylamino.

Examples of the C1-C3 alkylcarbonylamino group in the group of the 20 substituents include a linear group or a branched chain group, and a linear group is preferable. Specific examples include linear ones such as methylcarbonylamino (acetylamino), ethylcarbonylamino and n-propylcarbonylamino; branched chains such as isopropylcarbonylamino; Of these, acetylamino is preferred.

Examples of the C1-C6 alkyl group in the group of 20 substituents include a linear, branched or cyclic C1-C6, preferably C1-C4, and more preferably a C1-C3 alkyl group. A straight chain or a branched chain is preferable, and a straight chain is more preferable. Specific examples include linear ones such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl; isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl and the like. Branched-chain ones; cyclic ones such as cyclopropyl, cyclopentyl, cyclohexyl, etc .; and the like. Of these, methyl is preferred.

Examples of the halogen atom in the group of 20 substituents include a fluorine atom, a chlorine atom and a bromine atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

Examples of the C1-C6 alkylsulfonyl group in the group of 20 substituents include linear or branched C1-C6, preferably C1-C4, more preferably C1-C3 alkylsulfonyl group, which are linear. Those are preferable. Specific examples include linear chains such as methanesulfonyl (methylsulfonyl), ethanesulfonyl (ethylsulfonyl), n-propanesulfonyl (n-propylsulfonyl), n-butylsulfonyl, n-pentylsulfonyl, and n-hexylsulfonyl. Those; those having a branched chain such as isopropylsulfonyl and isobutylsulfonyl; and the like. Of these, methyl sulfonyl is preferred.

Examples of the C1-C6 alkylthio group in the group of 20 substituents include linear or branched C1-C6, preferably C1-C4, more preferably C1-C3 alkylthio group, and linear ones are used. preferable. Specific examples include linear chains such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio; isopropylthio, isobutylthio, t-butylthio, isopentylthio, isohexylthio and the like. Branched chain of; etc. Of these, methylthio is preferred.

When X is a sulfoanilino group, among the group of 20 substituents, a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group, and a di-C1-C4 alkylamino group. Groups, C1-C3 alkylcarbonylamino groups, C1-C6alkyl groups, nitro groups, halogen atoms, C1-C6 alkylsulfonyl groups, and C1-C6 alkylthio groups are preferred, with sulfo groups being particularly preferred.

When X is a carboxyanilino group, a sulfo group, a carboxy group, a hydroxy group, and a sulfamoyl group are preferable from the group of the 20 substituents.

When X is a phosphonoanilino group, it is preferable that the group selected from the group of the 20 substituents does not have a group.

When X is a sulfonaphthylamino-group, the sulfo group and the hydroxy group are preferable from the group of the 20 substituents.

When X is a carboxynaphthylamino-group or a phosphononaphthylamino-group, it is preferable that the group does not have a group selected from the group of the 20 substituents.

As a specific example of X in the above formula (1), a sulfoanilino group such as 2-sulfoanilino, 3-sulfoanilino, 4-sulfoanilino, 2,4-disulfoanilino, 2,5-disulfoanilino further has 0 or one sulfo group. Those; those in which the sulfoanilino group has one more carboxy group (or those in which the carboxyanilino group has one more sulfo group); 4-, such as 2-carboxy4-sulfoanilino, 2-carboxy-5-sulfoanilino, etc. A sulfoanilino group having an additional Cl-C6 alkoxy group, such as methoxy-2-sulfoanilino, 4-ethoxy-2-sulfoanilino, 4-ethoxy-6-sulfoanilino; sulfoanilino, such as 3-amino-4-sulfoanilino. A group having one more amino group; a sulfoanilino group having one more mono-C1-C4 alkylamino group, such as 4-methylamino-5-sulfoanilino; a 4-dimethylamino-5-sulfoanilino, etc. The sulfoanilino group has one more diC1-C4 alkylamino group; the sulfoanilino group has one more C1-C6 alkyl group, such as 2-methyl-5-sulfoanilino, 3-methyl-6-sulfoanilino; A sulfoanilino group having an additional arylamino group, such as 4-anilino-3-sulfoanilino; a sulfoanilino group having an additional one C1-C3 alkylcarbonylamino group, such as 4-acetylamino-2-sulfoanilino. The sulfoanilino group further has one or two halogen atoms, such as 2-chloro-5-sulfoanilino, 3,5-dichloro-4-sulfoanilino; 4-methylsulfonyl-2-sulfoanilino, 4-methylsulfonyl-5. -A sulfoanilino group having one more C1-C6 alkylsulfonyl group, such as sulfoanilino, 4-hexylsulfonyl-2-sulfoanilino; 4-methylthio-2-sulfoanilino, 4-hexylthio-2-sulfoanilino, etc. The sulfoanilino group further has one C1-C6 alkylthio group; 3-carboxy-4-hydroxy-5-sulfoanilino, 2-hydroxy-5-nitro-3-sulfoanilino, 2-methoxy-4-nitro-5-sulfoanilino. , 3-Methyl-6-methoxy-4-sulfoanilino, 2-hydroxy-3-acetylamino-5-sulfoanilino, etc. The nylino group has two more two groups selected from the group of the above 20 substituents; 2-carboxyanilino, 3-carboxyanilino, 4-carboxyanilino, 3,5-di. Those in which the carboxyanilino group has an additional 0 or 1 carboxy group, such as carboxyanilino; those in which the carboxyanilino group has an additional one sulfamoyl group, such as 4-sulfamoyl-2-carboxyanilino; 3-. A carboxyanilino group having one more hydroxy group, such as carboxy4-hydroxyanilino; a carboxyanilino group such as 4-hydroxy-3-sulfo5-carboxyanilino is a substituent of the 20 substituents. Those having two more groups of two types selected from the group; phosphonoanilino groups such as 2-phosphonoanilino, 3-phosphonoanilino, 4-phosphonoanilino; 4,8-disulfo2-naphthylamino, 1,5-disulfo-2. -Naphtylamino, 3,6-disulfo-1-naphthylamino, 5,7-disulfo-2-naphthylamino, 6,8-disulfo2-naphthylamino, 3,6,8-trisulfo-1-naphthylamino, 3 , 6,8-Trisulfo-2-naphthylamino, etc., where the sulfonaphthylamino group further has one or two sulfo groups; Those having one additional hydroxy group; 3,6-disulfo-8-hydroxy-1-naphthylamino, 8-chloro-3,6-disulfonaphthalene-1-ylamino, 6-nitro-4,8-disulfo- Examples thereof include those having two more groups in which the sulfonaphthylamino group is selected from the group of the 20 substituents, such as 2-naphthylamino; and the like.

Of these, 2-sulfoanilino, 3-sulfoanilino, 4-sulfoanilino, 2,4-disulfoanilino, 2,5-disulfoanilino, 3,6-disulfo-1-naphthylamino, 5,7-disulfo-2-naphthylamino, 6,8-Disulfo-2-naphthylamino, 3,6,8-trisulfo-1-naphthylamino are preferred, 4-sulfoanilino, 2,5-disulfoanilino, or 3,6,8-trisulfo-1-naphthylamino More preferably, 2,5-disulfoanilino is even more preferable.

In the formula (1), R is a hydrogen atom, a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono-C1-C6 alkylamino group; C1-C6 alkylamino group; mono-C6-C10 arylamino group; diC6-C10 arylamino group; C1-C3 alkylcarbonylamino group; ureido group; C1-C6 alkyl group; nitro group; cyano group; halogen atom; C1 -C6 alkylsulfonyl group; or alkylthio group;

Examples of the C1-C6 alkoxy group in R include a linear, branched or cyclic C1-C6, preferably C1-C4, and more preferably a C1-C3 alkyl group. A straight chain or a branched chain is preferable, and a straight chain is more preferable. Specific examples are linear ones such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy; to isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isopentyroxy, iso. Branched chains such as xyloxy; cyclic ones such as cyclopropoxy, cyclopentoxy, and cyclohexyloxy; and the like can be mentioned. Of these, methoxy or ethoxy is preferable, and methoxy is particularly preferable.

Examples of the monoCl-C4 alkylamino group in R include those having a linear or branched chain, and the range of the carbon number thereof is usually C1-C4, preferably C1-C3. Specific examples include linear ones such as methylamino, ethylamino, n-propylamino and n-butylamino; branched chains such as isopropylamino, isobutylamino, sec-butylamino and t-butylamino; etc. Can be mentioned.

Examples of the di-C1-C4 alkylamino group in R include a dialkylamino group having two independently of the alkyl moiety mentioned in the monoalkylamino group. Specific examples include dimethylamino, diethylamino, methylethylamino and the like.

Examples of the mono-C6-C10 arylamino group in R include a mono-C6-C10 aromatic amino group, preferably a phenylamino group or a naphthylamino group, and more preferably a phenylamino group.

Examples of the di-C6-C10 arylamino group in R include a diallylamino group having two independently of the aryls mentioned in the monoarylamino group. Preferred are those having the same aryl, more preferably two phenyls, and specific examples include diphenylamino.

Examples of the C1-C3 alkylcarbonylamino group in R include those having a straight chain or a branched chain, and those having a straight chain are preferable. Specific examples include linear ones such as methylcarbonylamino (acetylamino), ethylcarbonylamino and n-propylcarbonylamino; branched chains such as isopropylcarbonylamino;

Examples of the C1-C6 alkyl group in R include a linear, branched or cyclic C1-C6, preferably Cl-C4, and more preferably a C1-C3 alkyl group. A straight chain or a branched chain is preferable, and a straight chain is more preferable. Specific examples include linear ones such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl; isopropyl, isobutyl, Ssec-butyl, t-butyl, isopentyl, isohexyl and the like. Branched-chain ones; cyclic ones such as cyclopropyl, cyclopentyl, cyclohexyl, etc .; and the like. Of these, methyl is preferred.

Examples of the halogen atom in R include a fluorine atom, a chlorine atom and a bromine atom, and a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable.

Examples of the C1-C6 alkylsulfonyl group in R include a linear or branched C1-C6, preferably C1-C4, and more preferably a C1-C3 alkylsulfonyl group, and a linear group is preferable. Specific examples include linear chains such as methanesulfonyl (methylsulfonyl), ethanesulfonyl (ethylsulfonyl), n-propanesulfonyl (n-propylsulfonyl), n-butylsulfonyl, n-pentylsulfonyl, and n-hexylsulfonyl. Those; those having a branched chain such as isopropylsulfonyl and isobutylsulfonyl; and the like.

Examples of the C1-C6 alkylthio group in R include a linear or branched C1-C6, preferably C1-C4, and more preferably a Cl-C3 alkylthio group, and a linear group is preferable. Specific examples include linear chains such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio; isopropylthio, isobutylthio, t-butylthio, isopentylthio, isohexylthio and the like. Branched chain of; etc.

In the formula (1), group F is phenylene group; or 6-membered nitrogen-containing heteroaromatic ring group; represents a. Examples of the 6-member nitrogen-containing heteroaromatic ring group include a nitrogen-containing heteroaromatic ring group containing one nitrogen atom. Specific examples include pyridil.

In the 6-membered nitrogen-containing heteroaromatic ring, the bonding position with the alkylene represented by the number by "a" is not particularly limited, but it is preferable to bond with a carbon atom adjacent to the nitrogen atom. That is, when the group F is pyridyl, 2-pyridyl, 3-pyridyl, and 4-pyridyl are mentioned, with the substitution position of the nitrogen atom as the 1-position, and those bonded by the carbon atom adjacent to the nitrogen atom, that is, 2-pyridyl. Is preferable.

In the formula (1), when group F is phenylene group, among the R, a hydrogen atom, a sulfo group, a carboxy group, C1-C6 alkoxy group, C1-C6 alkyl group is preferably a halogen atom, a hydrogen atom, A sulfo group, a carboxy group, a methoxy group, a methyl group, a fluorine atom and a chlorine atom are more preferable, and a hydrogen atom, a sulfo group and a carboxy group are further preferable.

In the formula (1), when the group F is a 6-member nitrogen-containing heteroaromatic ring group, a hydrogen atom or a halogen atom is preferable, and a hydrogen atom is particularly preferable.

In the formula (1), the substitution position of R in the group F is not particularly limited.
When group F is phenylene group, a 1-position to the bonding position of the "(CH 2) _a ', the substitution position of R is 2-, 3-, or 4-position and the like, 4-position is preferred.
When the group F is a 6-membered nitrogen-containing heteroaromatic ring group, preferably pyridyl, _{the bonding positions of "(CH 2} ) a" and R are such that the nitrogen atom of the pyridine ring is at the 1-position, the former is at the 2-position, and the latter. 3rd, 4th, 5th, or 6th place is mentioned, and the former is 2nd place and the latter is 4th place.

In the formula (1), a _{represents the number of repetitions of "(CH 2} )", that is, the length of the alkylene, and is usually an integer of 1-6, preferably 1-4, more preferably 1-3, still more preferably. Is an integer of 1-2, particularly preferably 1.

The sums of b, C and b and c in the above formula (1) are all average values. b is 0.00 or more and less than 3.90, C 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 on average. At this time, the nitrogen-containing heteroaromatic rings in the rings A to D exceed 0.00 on average and 3.00 or less, and similarly, the benzene ring is 1.00 or more and less than 4.00.

Preferably, when the nitrogen-containing heteroaromatic ring in A to D is 0.20 or more and 2.00 or less and the benzene ring is 2.00 or more and 3.80 or less, b is 0.00 or more and 3.40 or less, and c is. 0.40 or more and 2.00 or less, and the sum of b and c is 2.00 or more and 3.80 or less.
More preferably, when the nitrogen-containing heteroaromatic ring in rings A to D is 0.50 or more and 1.75 or less, and the benzene ring is 2.25 or more and 3.50 or less, b is 0.35 or more and 3.05 or less. , C is 0.45 or more and 1.90 or less, and the sum of b and c is 2.25 or more and 3.50 or less.
More preferably, when the nitrogen-containing heteroaromatic ring in rings A to D is 0.75 or more and 1.50 or less and the benzene ring is 2.50 or more and 3.25 or less, b is 0.70 or more and 2.75 or less. , C is 0.50 or more and 1.80 or less, and the sum of b and c is 2.50 or more and 3.25 or less. As cb increases, the gas resistance tends to improve, but bronze is likely to occur. The number of b and c may be appropriately adjusted and a well-balanced ratio may be selected while considering gas resistance and bronze resistance.

In addition, both the unsubstituted sulfamoyl group and the substituted sulfamoyl group represented by the respective substitution numbers by b and c are groups to be substituted on the benzene ring when the rings A to D are benzene rings, and are rings. When A to D are 6-membered nitrogen-containing heteroaromatic rings, they are not substituted.

In addition, in this specification, b, c and the sum of b and c are described up to the second decimal place by rounding off three digits after the decimal point.

In the rings A to D, E, X, R, groups F, a, b and c, a porphyrazine-based compound in which preferable ones are combined is more preferable, and a porphyrazine-based compound in which more preferable ones are combined is further preferable. .. The same applies to more preferable ones, a combination of preferable ones and more preferable ones, and the like.

The porphyrazine-based compound of the present invention represented by the above formula (1) can also form a salt by utilizing sulfo, carboxy, phosphono and the like contained in the molecule. When forming a salt, the counter cation preferably forms a salt with each cation of an _{inorganic metal, ammonia (NH 3) or an organic base.}

Examples of the inorganic metal include alkali metals and alkaline earth metals. Examples of alkali metals include lithium, sodium, potassium and the like. Examples of the alkaline earth metal include calcium and magnesium.

Examples of the organic base include organic amines, for example, C1-C3 alkylamines such as methylamine and ethylamine, mono-, di- or tri-C1-C4 alkanols such as monoethanolamine, diethanolamine and trietanonolamine. Examples include amines.

Among the salts using the countercations of the above, preferred are alkali metal salts such as sodium, potassium and lithium; monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like. Salts with mono-, di- or tri-C1-C4 alkanolamines, and ammonium salts, but are not limited thereto.

Further, the salt of the porphyrazine-based compound of the present invention may change its physical properties such as solubility or the performance of the ink when used as an ink, particularly the performance related to the fastness, depending on the type of the salt. .. Therefore, it is also preferable to select the type of salt according to the performance of the target ink.

As the porphyrazine-based compound represented by the formula (1) or a salt thereof, a particularly preferable compound is a compound having the following combinations (a) to (f).
(B) As the nitrogen-containing heteroaromatic rings in rings A to D, pyridine rings fused at the 2- and 3-positions or at the 3- and 4-positions; or condensed rings at the 2- and 3-positions, respectively. Pyrazine rings are preferred.
As (b) E, linear C2-C4 alkylene is preferable.
(C) X includes a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group, a diC1-C4 alkylamino group and a C1-C3 alkylcarbonyl as substituents. It may have 0 to 2 substituents of 1 or 2 selected from the group consisting of an amino group, a nitro group, a halogen atom, a C1-C6 alkylsulfonyl group and an alkylthio group; a sulfoanilino group; a substituent. The carboxyanilino group may have 0 to 2 substituents selected from the group consisting of a sulfo group, a carboxy group, a hydroxy group, and a sulfamoyl group; or a phosphonoanilino group; or a substituent. As the group, a sulfonaphthylamino group which may have 0 to 2 substituents of 1 type or 2 types selected from a sulfo group and a hydroxy group is preferable.
(D) As R, a hydrogen atom; a sulfo group; a carboxy group; a C1-C6 alkoxy group; a C1-C6 alkyl group; or a halogen atom; is preferable.
The (E) group F, phenylene group; or a pyridyl group R is a hydrogen atom. (F) As a, 1 or 2 is preferable.

Specific examples of rings A to D, E, X, R, and group F, and the numbers of a, b, and c in the porphyrazine-based compound of the present invention represented by the formula (1) are shown in Table 1 below.
The following examples show representative examples in order to specifically explain the porphyrazine-based compound of the present invention, and the present invention is not limited to the following examples.

Further, when the nitrogen-containing heteroaromatic ring of rings A to D is a pyridine ring, a position isomer of a nitrogen atom or the like exists as described later, and it is obtained as a mixture of isomers in the synthesis of a porphyrazine-based compound. These isomers are difficult to handle, and it is also difficult to identify the isomers by analysis. Therefore, it is usually used as a mixture. The porphyrazine-based compound of the present invention also contains such a mixture. In the present specification, when these isomers and the like are represented by structural formulas without distinction, one representative structural formula is described for convenience. Regarding the numbers of b and c in the table, in order to avoid complication, the second digit after the decimal point is rounded off and up to one digit day is described. In Table 1, "2,3-pyrido" is a pyridine ring fused to a porphyrazine ring at the 2- and 3-positions, and "benzo" is a benzene ring fused to a porphyrazine ring, "2-pyridyl". "" Means that the nitrogen atom of the pyridine ring is at the 1-position _{and the bond position with "(CH 2} ) a" is at the 2-position. Also, for the "4-chloro" and the like in the R, group F is when the phenylene groups if the 1-position of the bonding position of the "(CH 2) _a '; group F is of the pyridine ring when the pyridyl When the nitrogen atom is at the 1st position; it represents the substitution position of R.

The porphyrazine-based compound of the present invention can usually be used without blending with other dyes, but in some cases, it may be used in combination with a known cyan-based dye as long as the effect of the present invention is not impaired. good.

When used in combination with a known cyanide dye, the dye to be blended may be C.I. I. Although a numbered triphenylmethane dye or phthalocyanine dye can be used, a phthalocyanine dye is preferable.

The method for producing the porphyrazine-based compound of the present invention represented by the formula (1) will be described.

The porphyrazine-based compound represented by the formula (1) is a porphyrazine compound represented by the following formula (1-1) and an organic amine represented by the following formula (1-2) in the presence of ammonia. It can be repeated by reacting with.

The porphyrazine compound represented by the following formula (1-1) is prepared by chlorosulfonylating the compound represented by the following formula (1-3) after synthesizing the compound represented by the following formula (1-3) according to a known method or a method thereof. Can be obtained by

That is, the compound represented by the following formula (1-3) can be synthesized, for example, according to the known methods disclosed in International Publication No. 2007/091631 and International Publication No. 2007/116933. These known documents do not disclose a method for producing a compound having less than 1 nitrogen-containing heteroaromatic ring in rings A to D. However, when the synthesis is carried out by a known nitrile method or Wyler method, the nitrogen-containing heteroaromatic ring dicarboxylic acid derivative used as a reaction raw material and the phthalic acid derivative are contained in the rings A to D by changing the compounding ratio. A compound represented by the formula (1-3) in which the number of nitrogen heteroaromatic rings is less than 1 can also be synthesized.

The obtained compound represented by the formula (1-3) is a mixture of positional isomers relating to the substitution position of the nitrogen-containing heteroaromatic ring in the rings A to D and the substitution position of the nitrogen atom in the nitrogen-containing heteroaromatic ring. Also, as described in the above-mentioned publicly known document.

In the formula (1-3), the rings A to D have the same meaning as in the above formula (1).

The porphyrazine compound represented by the formula (1-1) is prepared according to the same known method disclosed in the International Publication Pamphlet as in the synthesis of the compound represented by the formula (1-3), according to the formula (1-3). ) Can be obtained by chlorosulfonylating the compound. The throlosulfonyl group in the formula (1-1) is not introduced when the rings A to D introduced on the benzene ring in the rings A to D correspond to the nitrogen-containing heteroaromatic ring group. Since one chlorosulfonyl group is usually introduced on the benzene ring, the number of n in the formula (1-1) is less than or equal to the number of benzene rings in the rings A to D. Therefore, the number "n" of the chlorosulfonyl group in the formula (1-1) is 1.00 or more and less than 4.00 corresponding to the number of benzene rings of the porphyrazine compound represented by the formula (1-1). be.

As another method for synthesizing the porphyrazine compound represented by the formula (1-1), sulfo is obtained by condensing and closing a sulfophthalic acid having a sulfo group in advance and a nitrogen-containing heteroaromatic ring dicarboxylic acid derivative such as quinophosphate. Examples thereof include a method of synthesizing a porphyrazine compound having a group and then converting the sulfo group into a chlorosulfonyl group with an appropriate chlorinating agent such as thionyl chloride. In this case, it is introduced onto the porphyrazine compound represented by the formula (1-1) by selecting the one in which the substitution position of the sulfo group of sulfophthalic acid, which is a synthetic raw material, is at the 3-position or the 4-position. The substitution position of the sulfo group can be controlled. That is, when 3-sulfophthalic acid is used, the sulfo group is selectively introduced at the "α" position in the following formula (1-4), and when 4-sulfophthalic acid is used, the sulfo group is similarly introduced at the "β" position. Can be done. Unless otherwise specified in the present specification, the terms "α-position of porphyrazine ring" or "β-position of porphyrazine ring" mean the corresponding positions in the following formula (1-4).

On the other hand, the organic amine represented by the above formula (1-2) can also be produced by a known method. For example, 0.9 to 1.2 mol of substituted aniline or substituted naphthylamines corresponding to X and 1 mol of 2,4,6-trichloro-S-triazine (cyanul chloride) are added to water of an alkali metal such as sodium hydroxide. The reaction solution is adjusted to about pHl-5 with the oxide and reacted under the conditions of 0 to 40 ° C. for 2 to 12 hours to obtain a primary condensate. Next, _{0.9 to 1.5 mol of an amine called "H 2} N- (CH ₂ ) a-FR" was added, and the reaction solution was made to have a pH of about 5 to 10 with a hydroxide of an alkali metal such as sodium hydroxide. The secondary condensate is obtained by reacting at 5 to 80 ° C. for 0.5 to 12 hours. And 2 Tsugichijimigobutsu 1 mol of the obtained alkylene diamines corresponding to E and ( _"H 2 N-E-NH _2" as amine) 1-50 mol, approximately pH9~12,5~90 ℃, 0 . By reacting for 5 to 8 hours, the organic amine represented by the above formula (1-2) can be obtained. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; and the like are usually used for adjusting the pH of each linear reaction. The order of condensation may be appropriately determined according to the reactivity of various compounds to be condensed with cyanuric chloride, and is not limited to the above order.

The reaction between the porphyrazine compound represented by the formula (1-1) and the organic amine represented by the formula (1-2) is approximately pH 8 to 10, 5 to 70 in an aqueous solvent in the presence of ammonia. The reaction is carried out at ° C. for 1 to 20 hours to obtain the desired porphyrazine-based compound of the present invention represented by the formula (1). "Ammonia" used in the reaction usually means aqueous ammonia. However, any chemical substance that generates ammonia by neutralization or decomposition can be used. Examples of chemical substances that generate ammonia include those that generate ammonia by neutralization such as ammonium salts such as ammonium chloride and ammonium sulfate; those that generate ammonia by thermal decomposition of urea and the like; and ammonia gas. , Not limited to these. Ammonia water is preferable as the "ammonia", and concentrated ammonia water available as a commercially available product (usually, commercially available as approximately 28% ammonia water) or diluted with water as necessary before use. It's fine.

The amount of the organic amine represented by the formula (1-2) is a theoretical value [represented by the target formula (1) with respect to 1 mol of the porphyrazine compound represented by the usual formula (1-1). The number of moles of the organic amine represented by the calculated formula (1-2) required to obtain the value of c in the porphyrazine-based compound] is 1 mol or more, but the reactivity of the organic amine used, It depends on the reaction conditions and is not limited to these. Usually, it is about 1 to 2 mol, preferably about 1 to 2 mol, which is the theoretical value.

Further, the porphyrazine-based compound of the present invention represented by the above formula (1) is a reaction condition that does not require a particularly anhydrous condition from the above formula (1-1) and the compound represented by the formula (1-2). Synthesized below. Therefore, a compound in which a part of the chlorosulfonyl group in the formula (1-1) is hydrolyzed by water mixed in the reaction system and converted into a sulfonic acid is produced as a by-product, and as a result, the by-product is produced. It is theoretically possible to mix it with the target porphyrazine-based compound represented by the formula (1). However, it is difficult to distinguish between an unsubstituted sulfamoyl group and a sulfo group in mass spectrometry, and in the present invention, a formula (1-1) other than that reacted with an organic amine represented by the formula (1-2). All the chlorosulfonyl groups in the above are described as being converted into an unsubstituted sulfamoyl group.

Further, the porphyrazine-based compound represented by the above formula (1) is partially a copper porphyrazine ring (Pz) or a dimer (for example, Pz-L-Pz) or a dimer via a divalent linking group (L). The impurities forming the trimer may be by-produced and mixed in the reaction product.

Examples of the divalent linking group represented by _{L -SO 2 -, - SO 2} -NH-SO 2 - or the like have, by-products of these two L are combined in the case of a trimer It may be formed.

The porphyrazine-based compound of the present invention obtained as described above can be isolated as a solid by filtration separation or the like from the reaction solution in the final step of the synthesis reaction, which is precipitated by acidation or salting out. can. Salting out is preferably carried out, for example, in the range of acidic to alkaline, preferably pHl to 11. The temperature at the time of salting out is not particularly limited, but it is usually preferable to heat to 40 to 80 ° C., preferably 50 to 70 ° C., and then add sodium chloride or the like for salting out.

The porphyrazine-based compound synthesized by the above method is obtained as a free acid or a salt thereof. Examples of the method for isolating the porphyrazine-based compound as a free acid include acid analysis. As a method for isolating as a salt, salting out or when the desired salt cannot be obtained by salting out, for example, the obtained salt is converted into a free acid, and then a desired organic or inorganic base is added. Examples thereof include a method of salting out and a known salt exchange method.

In the present invention, the cyan ink preferably contains at least one lithium salt of an aromatic compound having a carboxyl group. As a result, even in the case of solid printing, it is possible to obtain a printed matter having excellent bronze resistance, and it is possible to suppress clogging at the nozzles. That is, if the cyan ink is an ink composition containing at least one of a porphyrazine-based compound represented by the above general formula (1) and a lithium salt of an aromatic compound having a carboxyl group, the cyan ink composition. Of course, even an ink composition having a color different from that of cyan, such as a black ink composition, is an ink composition having excellent bronze resistance. In order to prepare these various ink compositions, they can be used in combination with other conventionally known dyes.

The lithium salt of the aromatic compound having a carboxyl group used in the present invention may be any lithium salt of an aromatic compound having at least one carboxyl group in the molecular structure, but has a carboxyl group in the naphthalene skeleton. The lithium salt of the compound having is preferable, and the lithium salt of the compound having a carboxyl group at the 2-position of the naphthalene skeleton is more preferable. Further, a lithium salt of a compound having a carboxyl group and a −OR group in the naphthalene skeleton (R represents a hydrogen atom or an alkyl group of C1 to C6 is preferable, and among them, lithium of a compound having a carboxyl group at the 2-position of the naphthalene skeleton is preferable. Salts are more preferable. Specific examples of the lithium salt of the aromatic compound having a carboxyl group include 1-naphthoic acid, 2-naphthoic acid, 2-hydroxy-1-naphthoic acid and 1-hydroxy-2-naphthoic acid. , 3-Hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 3-methoxy-2-naphthoic acid, 3-ethoxy-2-naphthoic acid , 3-Propoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 6-ethoxy-2-naphthoic acid, 6-propoxy-2-naphthoic acid and other lithium salts.

The lithium salt of the aromatic compound having a carboxyl group can be added in the form of a salt and contained in the ink, and the aromatic compound having a carboxyl group and the base are separately added to the ink. It can also be contained therein.

The content of the lithium salt of these carboxyl group-containing aromatic compounds is determined by the type of the carboxyl group-containing aromatic compound and / or its salt, the type of dye, the type of solvent component, etc., but the entire ink composition It is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less with respect to the mass.

In the present embodiment, when the cyan ink contains the compound represented by the above formula (1), the robustness in a monochrome image is improved, and in particular, the heat resistance and the moisture resistance are improved.

11.2. Dyes other than phthalocyanine compounds represented by the general formula (1)

In the present embodiment, it is preferable that the cyan ink contains another phthalocyanine dye in addition to the compound represented by the above formula (1). In the present embodiment, when the cyan ink also contains other phthalocyanine dyes, the heat resistance and moisture resistance in a monochrome image are improved, and the gas resistance and color development are also improved.

In the present embodiment, other phthalocyanine dyes of the compound represented by the above formula (1) include the compound represented by the following general formula (3), C.I. I. Direct Blue 199, C.I. I. Direct blue 86 and the like can be mentioned.

In the above formula (3), Z _{1 to} Z ₄ independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group, and in particular, an alkyl group, an aryl group, or a heterocyclic group. Representing groups, each may further have a substituent. However, _{at least one of Z 1 to} Z ₄ has an ionic hydrophilic group as a substituent.

Of these, a substituted alkyl group, a substituted aryl group and a substituted heterocyclic group are preferable, a substituted alkyl group and a substituted aryl group are preferable, and a substituted alkyl group is most preferable.

The _{alkyl group represented by Z 1 to} Z ₄ is preferably an alkyl group having 1 to 30 carbon atoms. The _{cycloalkyl group represented by Z 1 to} Z ₄ is preferably a cycloalkyl group having 5 to 30 carbon atoms. The _{alkenyl group represented by Z 1 to} Z ₄ is preferably an alkenyl group having 2 to 30 carbon atoms. The aralkyl group represented by Z is preferably an aralkyl group having 7 to 30 carbon atoms. The _{aryl group represented by Z 1 to} Z ₄ is preferably an aryl group having 6 to 30 carbon atoms. As the _{heterocyclic group represented by Z 1 to} Z ₄ , an aromatic heterocyclic group is preferable, and examples of the preferred example thereof are pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, and triazole. , Thiazole, benzothiazole, isothiazole, benzisothiazole, thiathiazole and the like.

The ionic hydrophilic group as a substituent may be in the form of a salt, and examples of counterions forming the salt include alkali metal ions such as sodium ion, potassium ion and lithium ion.
Includes organic cations such as ammonium ion, tetramethylguanidinium ion, and organic and / or inorganic anions such as halogen ion, methanesulfonic acid ion, and benzenesulfonic acid ion.

Since the phthalocyanine compound represented by the formula (3) has at least one ionic hydrophilic group or a group having an ionic hydrophilic group as a substituent in one molecule, it is soluble in an aqueous medium. Or the dispersibility becomes good. From this point of view, the phthalocyanine compound represented by the above formula (3) preferably has at least two ionic hydrophilic groups in one molecule, and at least one of the plurality of ionic hydrophilic groups is preferable. Those having a sulfone group are more preferable, and among them, those having at least two sulfone groups in one molecule are most preferable.

M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide. Preferred as M are Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, as metal elements in addition to hydrogen atom. Examples thereof include Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb and Bi. Preferred examples of the oxide include VO and GeOO. Further, as the hydroxide, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like are preferably mentioned. Further, examples of the halide include AlCl, SiCl ₂ , VCl, Si (OH) ₂ , VOCl, FeCl, GaCl, ZrCl and the like. Among them, Cu, Ni, Zn, Al and the like are preferable, and Cu is the most preferable.

Further, in the phthalocyanine compound represented by the above formula (3), Pc (phthalocyanine ring) is a dimer (for example, Pc-ML-M-Pc) or 3 via L (divalent linking group). A quantity may be formed, and the plurality of Ms present at that time may be the same or different from each other.

The divalent linking group represented by L is an oxy group-O-, a thio group-S-, a carbonyl group-CO-, a sulfonyl group-SO _2- , an imino group-NH-, a methylene group-CH _2- , And a group formed by combining these are preferable.

In the formula (3), the molecular weight of the phthalocyanine compound is preferably in the range of 750 to 3000, more preferably in the range of 995 to 2500, and particularly preferably in the range of 995 to 2000, particularly in the range of 995 to 1800. Most preferred.

However, the phthalocyanine compound represented by the above formula (3) has a Pc (phthalocyanine ring) as a dimer (for example, Pc-ML-M-Pc) or 3 via L (divalent linking group). In the case of forming a weight, a preferable molecular weight, for example, a particularly preferable molecular weight is twice (in the case of a dimer) or three times (in the case of a trimer) a particularly preferable molecular weight (range of 995 to 1800) described above. ). Here, the preferable molecular weight of the above dimer or trimer is a value including the linking group L.

Among the above compounds, compounds in which M in the formula (3) is Cu and Z _{1 to} Z ₄ having an ionic hydrophilic group as a substituent are sulfoalkyl groups are more preferable, and the sulfone group is a salt. A compound in which the counter cation forming the salt is a lithium cation is preferable.

The phthalocyanine compound represented by the above formula (3) that can be used in the present invention is, for example, a phthalonitrile compound represented by the following formula (A) and / or a diiminoisoindoline derivative represented by the following formula (B). It is synthesized by reacting with a metal derivative represented by M- (Y) d. Specific examples of the metal derivative include copper chloride, copper bromide, copper iodide, nickel chloride, nickel bromide, nickel acetate, cobalt chloride, cobalt bromide, cobalt acetate, iron chloride, zinc chloride, zinc bromide, and iodide. Zinc b., Zinc acetate, vanadium chloride, vanadium oxytrichloride, palladium chloride, palladium acetate, aluminum chloride, manganese chloride, manganese acetate, acetylacetone manganese, manganese chloride, lead chloride, lead acetate, indium chloride, titanium chloride, tin chloride, etc. Can be mentioned.

このようにして得られる上記式（３）で表される化合物は通常、（ＳＯ_２−Ｚ_１）、（ＳＯ_２−Ｚ_２）、（ＳＯ_２−Ｚ_３）、（ＳＯ_２−Ｚ_４）の導入位置が異なる異性体の混合物となっている。さらに、置換基の異なる２種類以上の式（Ａ）及び／又は式（Ｂ）を用いて染料を調製する場合には、上記式（３）で表される化合物は、置換基の種類、位置が異なる染料混合物となっている。

The compound represented by the above formula (3) thus obtained is usually (SO _2- Z ₁ ), (SO _2- Z ₂ ), (SO _2- Z ₃ ), (SO _2- Z ₄ ). It is a mixture of isomers with different introduction positions. Further, when a dye is prepared using two or more kinds of formulas (A) and / or formulas (B) having different substituents, the compound represented by the above formula (3) is the type and position of the substituent. Is a different dye mixture.

Examples of the cyan dye used in the present invention include Japanese Patent Laid-Open Nos. 2002-249677, 2003-213167, 2003-213168, and compounds having the corresponding structures described in JP-A-2004-2670. However, the ones that are particularly preferred are those listed in the table below. The compounds listed in Table 5 can be synthesized by the methods described in the above publication. Of course, the starting compounds, dye intermediates and synthetic methods are not limited thereto.

In the above formula (3), M and Z _{1 to} Z ₄ are as shown in Table 5 below.

一般式（３−１）中、ＲはＳＯ_２（ＣＨ_２）_３ＳＯ_３Ｎａを表す。

In the present embodiment, the compound represented by the above formula (3) is particularly a mixture of the compound represented by the following general formula (3-1) and the compound represented by the following general formula (3-2). Is preferable.

In the general formula (3-1), R represents SO ₂ (CH ₂ ) ₃ SO ₃ Na.

In the compound represented by the above general formula (3-2), any two of R are SO ₂ (
CH ₂ ) _{represents 3} SO ₃ Li, the remaining two represent SO ₂ (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH ₃ , and are preferably a mixture of the following two structures. ..

In the present embodiment, the cyan ink further contains another phthalocyanine dye in addition to the compound represented by the above formula (1), and further forms an ink set together with the following magenta ink and yellow ink to form a monochrome image. In addition to improving heat resistance and moisture resistance, gas resistance and color development are improved.

The content of the dye is determined by the type of the dye contained, the type of the solvent component, etc., but is preferably 1.0% by mass or more and 10% by mass or less, preferably 2.0% by mass or less, based on the total weight of the ink composition. It is more preferably in the range of mass% or more and 5.0 mass% or less. Within the above range, the color development property or the image density on the recording medium can be ensured, the viscosity of the ink composition can be easily adjusted, and the characteristics such as ejection reliability and clogging can be easily ensured.

11.3. Water-soluble organic solvent In the present embodiment, the cyan ink preferably further contains a water-soluble organic solvent and / or a saccharide having a vapor pressure lower than that of pure water. By containing a water-soluble organic solvent and / or a saccharide, it is possible to suppress the evaporation of water and moisturize the ink in the inkjet recording method. Further, if it is a water-soluble organic solvent, the viscosity can be easily changed without improving the ejection stability or changing the ink characteristics. A water-soluble organic solvent refers to a medium having the ability to dissolve a solute, and is selected from organic and water-soluble solvents having a vapor pressure lower than that of water.

Examples of the water-soluble organic solvent include alkyl betaine, 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 monobutyl 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 butyl methyl 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, tert-butanol, iso-butanol, n-pentanol, 2-pen Alcohols or glycols such as tanol, 3-pentanol, and tert-pentanol, N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl2-pyrrolidone, 2-oxazolidone, 1 , 3-Dimethyl 2-imidazolidinone, dimethyl sulfoxide, sul Examples thereof include nitrogen-containing organic solvents such as horan and 1,1,3,3-tetramethylurea. As the saccharide, maltitol, sorbitol, gluconolactone, maltose and the like are preferable.

The above-mentioned water-soluble organic solvent may be used alone or in combination of two or more. The content of the water-soluble organic solvent is not particularly limited and can be appropriately determined as needed. For example, it is preferable to use alkyl betaine, glycerin, triethylene glycol, triethylene glycol monobutyl ether, and triethanolamine in order to improve the permeability, moisturizing property, and ejection stability of the ink into the recording medium. ..

The amount of the water-soluble organic solvent added is preferably 5% by mass or more and 40% by mass or less, more preferably 15% by mass or more and 35% by mass or less, and 20% by mass or more, based on the total mass of the ink. It is more preferably 30% by mass or less.

Among the above, it is preferable to contain triethylene glycol monobutyl ether as the water-soluble organic solvent, and the content of triethylene glycol monobutyl ether is 2.0% by mass or more and 15% by mass or less with respect to the total mass of the ink. It is more preferable, it is more preferably 2.5% by mass or more and 12.5% by mass or less, and further preferably 3.0% by mass or more and 10% by mass or less. When the amount of triethylene glycol monobutyl ether added is within the above range, the discharge stability is improved.

1.1.4. Surfactant In the present embodiment, the cyan ink preferably contains a surfactant. By containing the surfactant, the dynamic surface tension and wettability of the ink are adjusted, and the ejection stability is improved. Can be done.

The surfactant is not particularly limited, but is an acetylene glycol-based surfactant, a fluorine-based surfactant, and a silicone-based interface in that it adjusts the dynamic surface tension and wettability of the ink and improves ejection stability. Activators can be mentioned.

The acetylene glycol-based surfactant is not particularly limited, but is an acetylene glycol-based surfactant having an HLB value of 4 or less, an alkylene oxide adduct of acetylene glycol having 12 or more carbon atoms in the main chain, and the number of carbon atoms in the main chain. It is preferable to use an acetylene glycol-based surfactant such as acetylene glycol having a value of 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 the acetylene glycol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7. -Glycol alkylene oxide adduct, 2,4-dimethyl-5-decyne-4-ol and 2,4-dimethyl-5-decyne-4-ol alkylene oxide adduct, 2,5,8,11-tetra Examples thereof include the ethoxylated product of methyl-6-dodecyne-5,8-diol and the ethoxylated product of 5,8-dimethyl-6-dodecyne-5,8-diol. Among the alkylene oxide adducts of acetylene glycol, the ethylene oxide adduct of acetylene glycol and the propylene oxide adduct of acetylene glycol are preferable, and the ethylene oxide adduct of acetylene glycol is more preferable.

Commercially available products of acetylene glycol-based surfactants are not particularly limited, but for example, Orfin 104 series, Orfin E1010 E series (or higher), Orfin EXP4300 (carbon number 12-ethylene oxide adduct), Surfinol 61, Surfy. Noll 465, Surfinol 104S (HLB4), Surfinol 104PG50 (HLB4, 2,4,7,9-Tetramethyl-5-decyne-4,7-diol), Surfinol 420 (HLB4), Surfinol 82 (HLB4) ), Surfinol DF110D (HLB3, 2,5,8,11-tetramethyl-6-dodecin-5,8-diol), Surfinol MD-20 (HLB4), etc. ). These surfactants may be used alone or in combination of two or more.

The fluorosurfactant is not particularly limited, and is, for example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, per. Fluoroalkylamine oxide compounds can be mentioned. The commercially available fluorosurfactant is not particularly limited, but for example, S-144, S-145 (manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Florard-FC4430 (manufactured by Sumitomo 3M Ltd.). FSO, FSO-100, FSN, FSN-100, FS-300 (manufactured by DuPont); FT-250, 251 (manufactured by Neos Co., Ltd.) and the like. The fluorine-based surfactant may be used alone or in combination of two or more.

Examples of the silicone-based surfactant include polysiloxane-based compounds and polyether-modified organosiloxanes. The commercially available silicone-based surfactant is not particularly limited, but 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 , 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 is 0.2% by mass or more and 1.2% by mass or less, based on the total mass of the ink composition. Is more preferable, and more preferably 0.3% by mass or more and 1.0% by mass or less. When the content of the surfactant is within the above range, the discharge stability is further improved.

1.1.5. Water In this embodiment, the cyan ink may further contain water.

Examples of the water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, it is possible to prevent the growth of mold and bacteria when the ink is stored for a long period of time. This further improves storage stability.

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

1.1.6. pH regulator In this embodiment, the cyan ink may contain a pH regulator. The pH adjuster can facilitate the adjustment of the pH value of the ink. The pH adjuster is not particularly limited, and is, for example, an inorganic acid such as sulfuric acid, hydrochloric acid, or nitrate, an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or ammonia, triethanolamine, diethanolamine, or monoethanolamine. , Organic bases such as tripropanolamine, organic acids such as adipic acid, citric acid, succinic acid and the like. The pH adjuster may be used alone or in combination of two or more.

1.1.7. Other Ingredients In the present embodiment, the cyan ink is a dissolution aid and a viscosity regulator in order to maintain good storage stability and ejection stability from the head, to improve clogging, or to prevent deterioration of the ink. Various additives such as agents, pH regulators, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents to capture metal ions that affect dispersion may be added as appropriate. can.

1.1.8. Ink Preparation Method In the present embodiment, cyan ink is obtained by mixing the above-mentioned components in an arbitrary order and filtering or the like as necessary to remove impurities. As a method of mixing each component, a method of sequentially adding materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirring and mixing is preferably used. As the filtration method, centrifugal filtration, filter filtration and the like can be performed as needed.

1.1.9. Physical Characteristics of Ink In this embodiment, the surface tension of cyan ink at 20 ° C. is preferably 20 mN / m or more and 50 mN / m, preferably 25 mN / m, from the viewpoint of the balance between recording quality and reliability as an inkjet ink. It is more preferably 40 mN / m or less. To measure the surface tension, use an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Surface 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 by.

From the same viewpoint, in the present embodiment, the viscosity of the cyan ink at 20 ° C. is preferably 1 mPa · s or more and 8 mPa · s or less, and more preferably 2 mPa · s or more and 6 mPa · s or less. The viscosity can be measured using a vibration viscometer VM-100AL (trade name, manufactured by Yamaichi Electric Co., Ltd.).

Further, in order to stably dissolve the amount of the aromatic compound having a predetermined dye and carboxyl group and / or a salt thereof, the pH of the cyan ink at 20 ° C. is preferably 8.0 or more. Further, considering the corrosion resistance with various members in contact with the cyan ink, the pH of the cyan ink is preferably 10.5 or less. In order to achieve both of these matters better, it is more preferable to adjust the pH of the ink composition to 8.5 to 10.0.

1.2. Magenta Ink In the ink set according to the present embodiment, the magenta ink is characterized by containing a compound having a xanthene skeleton or a salt thereof. In the ink set according to the present embodiment, the magenta ink contains a compound having a xanthene skeleton or a salt thereof, so that the ink set has excellent color development and excellent heat resistance and moisture resistance in monochrome images.

一般式（２）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。 1.2.1. Compound having a xanthene skeleton In the present embodiment, the compound having a xanthene skeleton is preferably a compound represented by the following general formula (2).

In the general formula (2), 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 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or absent, respectively. Substituent 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 , Substituent or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, or substituted or unsubstituted alkyl Represents an arylaminocarbonyl group.

In the present embodiment, since magenta ink is a compound represented by the above general formula (2) as a dye, an ink set having excellent heat resistance and moisture resistance in a monochrome image is obtained. Further, by including the compound represented by the general formula (4) described later, gas resistance in a light-colored region having a low recording density can be improved.

Hereinafter, the compound represented by the above general formula (2) will be described. For the compound represented by the general formula (2), the description in paragraph No. 0015-0084 of JP-A-2016-41801 is cited.

First, a specific example of the substituent used in the compound represented by the general formula (2) is 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, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, Examples thereof include an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, and an ionic hydrophilic group. These substituents may be further substituted, and examples of further substituents include groups selected from the substituent group A described above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include linear, branched, cyclically substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclostructures having many ring structures. Alkyl groups among the substituents described below (for example, an alkoxy group and an alkyl group of an alkylthio group) also represent an alkyl group of such a concept.
The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, 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 and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, a cyclohexyl group, a cyclopentyl group, 4 Examples thereof include the -n-dodecylcyclohexyl group, 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. Examples of the removed monovalent group include a bicyclo [1,2,2] heptane-2-yl group, a bicyclo [2,2,2] octane-3-yl group and the like.

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, cyclically substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups.
The alkenyl group preferably includes a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group and the like, and the cycloalkenyl group is preferable. Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group from which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed, for example, a 2-cyclopenten-1-yl group. Examples thereof include 2-cyclohexene-1-yl group, and examples of the bicycloalkenyl group include 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 from which one hydrogen atom of a bicycloalkene having one is removed, for example, a bicyclo [2,2,1] hept-2-en-1-yl group, a bicyclo [2,2,2] octo-2- Examples thereof include an en-4-yl group.

The alkynyl group preferably includes a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group and the like.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an 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 the number of carbon atoms. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups, such as 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like. Examples of non-aromatic heterocyclic groups include morpholinyl groups and the like.

The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group or a 2-methoxyethoxy group. And so on.

The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, 2 -Examples include a tetradecanoylaminophenoxy group.

The silyloxy group is preferably a substituted or unsubstituted silyloxy group having 0 to 20 carbon atoms, for example, a trimethylsilyloxy group, a diphenylmethylsilyloxy group and the like.

The heterocyclic oxy group preferably includes a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group and the like.

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

The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, 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, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group. And so on.

The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, or pn-hexadecyloxy. Examples thereof include a 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, and a substituted or non-substituted amino group having 6 to 30 carbon atoms. Examples thereof include a substituted anilino group, for example, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, a triazinylamino group and the like.

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, for example, an acetylamino group. Examples thereof include a pivaloylamino group, a lauroylamino group, a benzoylamino group, a 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, for example, a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, or an N, N-diethylaminocarbonylamino group. , Morphorinocarbonylamino group and the like.

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

The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, or an 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, for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, Nn-. Examples thereof include an 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, for example, a methylsulfonylamino group. , Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group and the like.
The alkylthio group preferably includes a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, a methylthio group, an ethylthio group, an n-hexadecylthio group and the like.

The arylthio group preferably includes a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group and the like.

The heterocyclic thio group preferably includes a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, a 2-benzothiazolylthio group, a 1-phenyltetrazole-5-ylthio group and the like.

The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, an N-ethylsulfamoyl group, an N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsul. Examples thereof include a famoyl group, an N-acetylsulfamoyl group, an N-benzoyl sulfamoyl group, an N- (N'-phenylcarbamoyl) sulfamoyl group and the like.

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, for example, 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, for example, a methylsulfonyl group or an ethylsulfonyl group. , Penylsulfonyl 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 no substituted group having 2 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group at the substituted carbon atom, such as an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxyphenylcarbonyl group, 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, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, pt-. Examples thereof include a butylphenoxycarbonyl group.

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

The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, N, N-di-n-octyl. 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, for example, a phenylazo group or p-chlorophenylazo. Groups, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group and the like can be mentioned.

The imide group preferably includes an N-succinimide group, an N-phthalimide group and the like.

The phosphino group preferably includes a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, for example, a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group and the like.

The phosphinyl group preferably includes a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group and the like.

The phosphinyloxy group preferably includes a substituted or unsubstituted phosphinyloxy group having 0 to 30 carbon atoms, for example, a diphenoxyphosphinyloxy group, a dioctyloxyphosphinyloxy group and the like.

The phosphinylamino group preferably includes a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, for example, a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.

The silyl group preferably includes a substituted or unsubstituted silyl group having 0 to 30 carbon atoms, for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group and the like.

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, a quaternary ammonium group and the like. Particularly preferably, it is a sulfo group or a carboxyl group. Further, the carboxyl group, the phosphono group and the sulfo group may be in the salt state, and examples of the counter cations forming the salt include alkali metal ions such as ammonium ion, lithium ion, sodium ion and potassium ion, and tetramethylammonium. It contains organic cations such as ions, tetramethylguanidium ions, and tetramethylphosphonium, and is preferably a lithium salt, a sodium salt, a potassium salt, or an ammonium salt, and more preferably a sodium salt or a mixed salt containing a sodium salt as a main component. Ammonium salts are most preferred.

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

<Compound represented by the general formula (2)>
The compound represented by the following general formula (2) will be described.

In the above formula (2), 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 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or absent, respectively. Substituent 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 , Substituent or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, or substituted or unsubstituted alkyl Represents an arylaminocarbonyl group.

The compound represented by the formula (2) 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 (2) exhibits high saturation, excellent printing density, light resistance, and gas resistance by having such a structure.

In the above formula (2), 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 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 When R ²⁰ is represented by a substituent, the substituent includes a substituent selected from the above-mentioned Substituent Group A.

In the above formula (2), R ¹ , R ⁵ , R ⁶ and R ¹⁰ are independently hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or absent, respectively, 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, and more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted. It is an aryl group, a substituted or unsubstituted alkoxy group, and particularly preferably a substituted or unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable. Further, as the substituent when each group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

In the above formula (2), R ⁴ and R ⁹ are independently hydrogen atom, substituted or absent from the viewpoints of availability of raw materials, ease of synthesis, light resistance, gas resistance, printing concentration, and saturation. Substituent 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 arylureid group, sulfo group, carboxyl group, Alternatively, it preferably represents a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonyl. It is an amino group, a substituted or unsubstituted alkyl ureido group, a substituted or unsubstituted aryl ureido group, or a sulfo group, and a hydrogen atom or a sulfo group is particularly preferable. Further, as the substituent when each group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

In the above formula (2), R ³ and R ⁸ are independently hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted, respectively, from the viewpoint of availability of raw materials and ease of synthesis. Alternatively, 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. It preferably represents a group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkyl ureido group, a substituted or unsubstituted aryl ureido group, a sulfo group, a carboxyl group, or a halogen atom, more preferably a hydrogen atom. , Substituent or unsubstituted alkyl group, or sulfo group, particularly preferably substituted or unsubstituted alkyl group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable. Further, as the substituent when each group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

In the above formula (2), R ¹¹ , R ¹⁴ , R ¹³ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independent hydrogen atoms from the viewpoint of availability of raw materials and ease of synthesis. , Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, hydroxy group, halogen atom, or sulfo group. It is preferably a hydrogen atom, a hydroxy group, a halogen atom, or a sulfo group, and particularly preferably a hydrogen atom. Further, as the substituent when each group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

In the above formula (2), R ¹² and R ¹⁵ are independently hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, and halogens, respectively, 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. Further, as the substituent when each group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

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 the above formula (2). ^{It is preferable that at least one of 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. Examples of the counter cation of these ionic hydrophilic groups include alkali metal cations such as protons, lithium ions, sodium ions and potassium ions, ammonium ions and the like, but from the viewpoint of ease of handling as a dye powder, alkali metals. It is preferably a cation.

In the formula (2), R ¹⁰¹ and R ¹⁰² are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted alkylsulfonyl groups, respectively. 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. 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, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is preferable. Is more preferable. When the alkyl group has a substituent, the substituent includes a substituent selected from the above-mentioned Substituent Group A, an aryl group is preferable, and a phenyl group is particularly preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted aryl group, an aryl group having 6 to 14 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is further preferable. .. Further, as the substituent when the aryl group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted heterocyclic group, a triazine group, a thiazolyl group, a benzothiazolyl group, or a thiadiazolyl group is preferable as the heterocyclic group. When the heterocyclic group has a substituent, the substituent includes a substituent selected from the above-mentioned Substituent Group A, and a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group are preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted alkylsulfonyl group, the alkylsulfonyl group having 1 to 6 carbon atoms is preferable, the alkylsulfonyl group having 1 to 3 carbon atoms is more preferable, and methyl. A sulfonyl group is more preferred. Further, as the substituent when the alkylsulfonyl group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted arylsulfonyl group, the arylsulfonyl group having 6 to 14 carbon atoms is preferable, the arylsulfonyl group having 6 to 10 carbon atoms is more preferable, and phenyl. A sulfonyl group is more preferred. Further, as the substituent when the arylsulfonyl group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned, and a carboxyl group is particularly preferable.
When 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, an alkyl group having 1 to 4 carbon atoms is preferable, and an isopropyl group is more preferable. Further, as the substituent when the alkoxycarbonyl group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted aryloxycarbonyl group, the aryloxycarbonyl group is preferably represented by ^{-COOR 202.} Here, 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. When the aryloxycarbonyl group has a substituent, the substituent includes a substituent selected from the above-mentioned 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, and a methyl group, an ethyl group, an isopropyl group, or a hexyl group. , 2-Ethylhexyl group, dodecyl group, cyclohexyl group are more preferable, and isopropyl group is particularly preferable. When the monoalkylaminocarbonyl group has a substituent, the substituent includes a substituent selected from the above-mentioned substituent group A, 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 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.
When the dialkylaminocarbonyl group has a substituent, the substituent includes a substituent selected from the above-mentioned substituent group A, which is a carboxyl group, preferably an alkyloxycarbonyl group having 2 to 6 carbon atoms, and more. Alkyloxycarbonyl groups such as ethyloxycarbonyl groups are particularly preferred.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted monoarylaminocarbonyl group, the monoarylaminocarbonyl group is preferably represented by ^{−CONHR 206.} Here, 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. When the monoarylaminocarbonyl group has a substituent, the substituent includes a substituent selected from the above-mentioned substituent group A, and a carboxyl group, a hydroxyl group, a phosphono group, preferably an alkoxy having 1 to 6 carbon atoms. It is a group, and more preferably an alkoxy group such as a cyclohexyloxy group is particularly preferable.
When R ¹⁰¹ and R ¹⁰² represent a substituted or unsubstituted diarylaminocarbonyl group, 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. Further, as the substituent when the diarylaminocarbonyl group has a substituent, a substituent selected from the above-mentioned Substituent Group A can be mentioned.

From the viewpoints of saturation, heat resistance, moisture resistance, light resistance and gas resistance, R ¹⁰¹ and R ^{102 are preferably 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 mono. An arylaminocarbonyl 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, 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 An unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, or a substituted or unsubstituted diarylaminocarbonyl group.

Specific examples of the compound represented by the formula (2) are given below, but the present invention is not limited thereto. In the structural formulas of the specific compounds below, 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.

Dyes, which are compounds represented by the formula (2), have high saturation and excellent color development, especially in a wavelength range with high lightness, and tend to suppress deterioration of color development as compared with conventional dyes. Yes, it tends to have excellent gas resistance. Therefore, by using the compound represented by the above formula (2) as the dye of magenta ink, an ink set having excellent heat resistance and moisture resistance in a monochrome image can be obtained.

In the compound represented by the formula (2), it is preferable that R ¹ , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ are independently alkyl groups having 1 to 6 carbon atoms. In this case, even when used as a light magenta ink having a low dye concentration, the ink set has excellent heat resistance and moisture resistance in a monochrome image.

In the present embodiment, the content of the compound represented by the formula (2) in the magenta ink is preferably 0.6% by mass or more, preferably 0.8% by mass or more, based on the total mass of the ink. It is more preferably present, and further preferably 1.0% by mass or more. The content of the compound represented by the formula (2) in magenta ink is preferably 2.0% by mass or less, and preferably 1.5% by mass or less, based on the total mass of the ink. It is more preferably 1.2% by mass or less, and even more preferably 1.2% by mass or less.

When the content of the compound represented by the formula (2) is within the above range, the ink set has excellent heat resistance and moisture resistance in a monochrome image.

1.2.2. Magenta dyes other than compounds having a xanthene skeleton In this embodiment, the magenta ink preferably contains a magenta dye other than the compound represented by the above general formula (2) as the dye. When the magenta ink contains a magenta dye other than the compound represented by the above general formula (2), the color development property and the gas resistance are improved, and the ink set has excellent fastness in a monochrome image.

In the present embodiment, the magenta dye other than the compound having a xanthene skeleton is preferably one or more selected from anthrapyridone-based dyes, reactive dyes and azo-based dyes. Since the magenta dye other than the compound having a xanthene skeleton is at least one selected from anthrapyridone dyes, reactive dyes and azo dyes, the ink set has excellent fastness such as heat resistance and moisture resistance in monochrome images. Become.

As the anthrapyridone dye, a dye represented by the following formula (M-1) is preferable. In the present embodiment, the magenta ink contains the dye represented by the following formula (M-1), so that the ink set has more excellent fastness such as heat resistance and moisture resistance in a monochrome image.

一般式（Ｍ−１）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式（Ｍ−１−１）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（Ｍ−１−１）中、Ｒ^Ｍ１は、水素原子又はアルキル基を表す。 <Dye represented by the general formula (M-1)>
Hereinafter, the dye represented by the general formula (M-1) will be described in detail. The dye represented by the general formula (M-1) may form a salt.

In the general formula (M-1), ^AM1 is 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 formula (M-1-1). ^{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 the general formula (M-1-1), ^RM1 represents a hydrogen atom or an alkyl group.

In the above general formula (M-1), ^AM1 is preferably an alkylene group having 1 or 2 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.

In the general formula (M-1), 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 good effect of improving moisture resistance, and a phenoxy group substituted with two carboxy groups has a better moisture resistance, and is particularly preferable.

Specific examples of the phenoxy group substituted with a sulfo group or a carboxy group in the general formula (M-1) include 4-sulfophenoxy, 2,4-disulfophenoxy, 4-carboxyphenoxy, and 3,5-dicarboxy. It is phenoxy, more preferably 4-carboxyphenoxy, 3,5-dicarboxyphenoxy, and even more preferably 3,5-dicarboxyphenoxy.

Examples of the salt of the compound represented by the general formula (M-1) include an ammonium salt and an alkali metal salt.

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

The content of the dye represented by the general formula (M-1) is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, based on the total mass of the magenta ink. , 0.8% by mass or more is more preferable. The content of the dye represented by the general formula (M-1) is preferably 3.0% by mass or less, preferably 2.4% by mass or less, based on the total mass of the ink composition. Is more preferable, and 1.6% by mass or less is further preferable. When the content of the dye represented by the formula (M-1) is within the above range, the ink set has excellent fastness such as heat resistance and moisture resistance in a monochrome image.

<Dye represented by the general formula (M-2)>

As the azo dye, for example, a dye represented by the following general formula (M-2) is preferable. By containing the dye represented by the following general formula (M-2) in the ink composition according to the present embodiment, an ink set having more excellent fastness such as heat resistance and moisture resistance in a monochrome image can be obtained.

上記一般式（Ｍ−２）中、Ａ^Ｍ２は、５員複素環基を表し、
Ｂ^Ｍ２１及びＢ^Ｍ２２は、各々−ＣＲ^Ｍ２１＝、−ＣＲ^Ｍ２２＝を表すか、あるいはいずれか一方が窒素原子，他方が−ＣＲ^Ｍ２１＝又は−ＣＲ^Ｍ２２＝を表し、
Ｒ^Ｍ２３、Ｒ^Ｍ２４は、各々独立して、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、又はスルファモイル基を表わし、Ｒ^Ｍ２３，Ｒ^Ｍ２４は更に置換基を有していてもよく、
Ｇ^Ｍ２、Ｒ^Ｍ２１、Ｒ^Ｍ２２は、各々独立して、水素原子、ハロゲン原子、脂肪族基、芳香族基、複素環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アルキル基又はアリール基又は複素環基で置換されたアミノ基、アシルアミノ基、ウレイド基、スルフアモイルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルキル及びアリールスルホニルアミノ基、アリールオキシカルボニルアミノ基、ニトロ基、アルキル及びアリールチオ基、アルキル及びアリールスルホニル基、アルキル及びアリールスルフィニル基、スルファモイル基、スルホ基、又はヘテロ環チオ基を表し、Ｇ^Ｍ２、Ｒ^Ｍ２１、Ｒ^Ｍ２２は、更に置換されていてもよく、
Ｒ^Ｍ２１とＲ^Ｍ２３、あるいはＲ^Ｍ２３とＲ^Ｍ２４が結合して５〜６員環を形成してもよい。 The dye represented by the general formula (M-2) may form a salt.

In the above general formula (M-2), ^AM2 represents a 5-membered heterocyclic group and represents.
B ^M21 and B ^M22 represent -CR ^M21 =, ^{-CR M22} =, respectively, or one represents a nitrogen atom and the other represents -CR ^M21 = or -CR ^M22 =.
^RM23 and ^RM24 are independent of hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, respectively. or a sulfamoyl ^group, R ^{M23, R M24} may have a substituent,
G ^{M2, R} M21, ^{R M22} are independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group , Acrylic group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or heterocyclic group. Substituted amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and arylthio group, alkyl and arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio ^{group, G M2, R M21, R} M22 may be further substituted,
^RM21 and ^RM23 , or ^RM23 and ^RM24 may be combined to form a 5- to 6-membered ring.

In the general formula (M-2), examples of the 5-membered heterocyclic group include a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, a benzothiazole ring, a benzoxazole ring, and a benzoisothiazole ring. And each heterocyclic group may further have a substituent. Further, among the heterocycles, the pyrazole ring is preferable.

In the general formula (M-2), in ^RM21 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.

In the general formula (M-2), in ^RM22 , an aliphatic group is preferable, and a methyl group, an ethyl group, a propyl group which may be branched, or a butyl group which may be branched is more preferable.

In the general formula (M-2), ^RM23 and ^RM24 are each independently a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and a carbamoyl group. , Alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group. ^RM23 and ^RM24 may further have a substituent.

In the general formula (M-2), in ^RM23 , an aromatic group is preferable, and specific examples thereof include a benzene ring group and a naphthalene ring group. In the above ^RM24 , a heterocyclic group is preferable, and specific examples thereof include a benzothiazole ring group.

In formula ^{(M2), G M2, R} M21, R M23 are independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group , Alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group substituted with a group or an aryl group or a heterocyclic group. , Nitro groups, alkyl and arylthio groups, alkyl and arylsulfonyl groups, alkyl and arylsulfinyl groups, sulfamoyl groups, sulfo groups, or heterocyclic thio groups. ^RM23 and ^RM24 may be further substituted. Further, ^RM21 and ^RM23 , or ^RM23 and ^RM24 may be combined to form a 5- to 6-membered ring.

一般式（Ｍ−２１）中、Ｒ^Ｍ２５、Ｒ^Ｍ２６、Ｒ^Ｍ２７、Ｒ^Ｍ２８、Ｒ^Ｍ２９は、水素原子、アルキル基、スルホ基又はその塩を表す。一般式（Ｍ−２１）において、Ｒ^Ｍ２５、Ｒ^Ｍ２９は、共にアルキルであるときは、該アルキル基を構成する炭素数の合計が３以上であって、それらに置換基を有していてもよい。Ｘ^Ｍ２は水素原子、脂肪族基、芳香族基、又は複素環基を表し、Ｙ^Ｍ２及びＺ^Ｍ２は各々独立して、水素原子、脂肪族基、芳香族基、複素環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、又はスルファモイル基を表す。各基は更に置換基を有していてもよい。また、Ｒ^Ｍ２５〜Ｒ^Ｍ２９にスルホ基が含まれる場合には−ＳＯ_３Ｍの形となっている。その場合、Ｍとしては、アルカリ金属原子が好ましく、より好ましくはＬｉ及びＮａの少なくとも１種である。 Among the dyes represented by the general formula (M-2), the compounds represented by the following general formula (M-21) are preferable.

In the general formula (M-21), ^RM25 , ^RM26 , ^RM27 , ^RM28 , ^RM29 represent a hydrogen atom, an alkyl group, a sulfo group or a salt thereof. In the general formula (M-21), ^{when both RM25} and ^RM29 are alkyl, even if the total number of carbon atoms constituting the alkyl group is 3 or more and they have a substituent. good. X ^M2 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and Y ^M2 and Z ^M2 are independently hydrogen atoms, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, and the like. Represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent. ^Further, if it contains a sulfo group in R M25 ^{to R M29} has a form of -SO ₃ M. In that case, M is preferably an alkali metal atom, more preferably at least one of Li and Na.

In the general formula (M-21), in X ^M2 , an aromatic group, an alicyclic group, and a heterocyclic group are particularly preferable, and specific examples thereof include, for example, a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclo. Octane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole ring, benzoimidazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, oxane ring, sulfolane ring and thian ring. And so on. Of these, heterocycles are more preferred.

In the general formula ^(M-21), preferred examples of ^{Y M2} and ^{Z M2} is the same as the preferred examples of ^{R M23} and ^{R M24} in the dye (M2).

一般式（Ｍ−２２）中、Ｒ^Ｍ２５、Ｒ^Ｍ２６、Ｒ^Ｍ２７、Ｒ^Ｍ２８、Ｒ^Ｍ２９、Ｒ^Ｍ２１０、Ｒ^Ｍ２１１、Ｒ^Ｍ２１２、Ｒ^Ｍ２１３、Ｒ^Ｍ２１４は、水素原子、アルキル基、スルホ基又はその塩を表し、Ｍ^Ｍ２は、水素原子又はアルカリ金属原子を表す。また、Ｒ^Ｍ２５及びＲ^Ｍ２９が共にアルキル基である場合には、そのアルキル基を構成する炭素数の合計が３以上であって、それらはさらに置換基を有してもよく、Ｒ^Ｍ２１０及びＲ^Ｍ２１４が共にアルキル基である場合には、そのアルキル基を構成する炭素数の合計が３以上であって、それらはさらに置換基を有してもよい。 Among the compounds represented by the general formula (M-21), the compound represented by the following general formula (M-22) is particularly preferable because it has excellent color-developing property and gas resistance.

In the general formula ^{(M-22), R M25} , R M26, R M27, R M28, R M29, R M210, R M211, R M212, R M213, R M214 is a hydrogen atom, an alkyl group, a sulfo group or a represents salt, M ^M2 represents a hydrogen atom or an alkali metal atom. When ^{both RM25} and ^RM29 are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may further have a substituent, ^{and RM210} and R may further have a substituent. ^When both M214 are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may further have a substituent.

Among the compounds represented by the general formula (M-22), the compound represented by the following general formula (M-23) is particularly preferable.

Examples of the reactive dye include C.I. I. Reactive Red 141 is mentioned. In the present embodiment, the magenta ink contains the dye represented by the following general formula (4), so that the ink set has more excellent fastness such as heat resistance and moisture resistance in a monochrome image.

The ink composition according to the present embodiment may contain dyes other than the above in order to adjust the color tone and the like, as long as the characteristics such as heat resistance and moisture resistance are not significantly impaired.

1.2.3. Other Ink In the ink set according to the present embodiment, the magenta ink may contain other components other than the dye such as a water-soluble organic solvent, a surfactant, water, and a pH adjuster, similarly to the above-mentioned cyan ink. Since the components other than the dye are the same as those of cyan ink, the description thereof will be omitted. The same applies to the ink preparation method and physical properties.

1.3. Yellow ink In the ink set according to the present embodiment, the yellow ink contains a compound having a dimeric disazo structure formed by binding via a triazine skeleton or a salt thereof. When the ink set according to the present embodiment contains the above-mentioned dye, the ink set has excellent fastness such as heat resistance and moisture resistance in a monochrome image.

The yellow ink is a compound having a dimeric disazo structure formed by binding via a triazine skeleton, for example, a first yellow dye represented by the following general formula (Y-1), the following general formula (Y). The second yellow dye represented by -2), C.I. I. Direct Yellow 86 and C.I. I. Direct yellow 132 can be mentioned.

In the present embodiment, the yellow ink is any compound having the above-mentioned dimer dysazo structure, and further, by forming an ink set together with the above-mentioned cyan ink and magenta, the heat resistance and moisture resistance in a monochrome image are well-balanced. Can be improved. Therefore, an image having an excellent color balance can be obtained, and the fading balance becomes excellent, so that the image quality of the printed matter can be kept good for a longer period of time.

As the yellow ink, one or more of the above dyes can be used, and it is preferable to use a mixture of two or more. Further, a dye other than the above may be further contained in the yellow ink. The content of the dye in the yellow ink is preferably 0.1% by mass or more and 10.0% by mass or less, and 1.0% by mass or more and 5.0% by mass or less, based on the total mass of the yellow ink. It is more preferably 2% by mass or more and 4.0% by mass or less.

In the ink set according to the present embodiment, the yellow ink may contain other components other than the dye such as a water-soluble organic solvent, a surfactant, water, and a pH adjuster, similarly to the above-mentioned cyan ink. Since the components other than the dye are the same as those of cyan ink, the description thereof will be omitted. The same applies to the ink preparation method and physical properties.

1.4. Ink set The ink set according to the present embodiment is an ink set containing cyan ink, magenta ink, and yellow ink, and includes the above cyan ink, magenta ink, and yellow ink. Moreover, in this embodiment, you may have ink other than these. By recording using this ink set, it is possible to improve the robustness such as heat resistance and moisture resistance in a monochrome image in a well-balanced manner.

The ink set according to the present embodiment can be housed in an ink cartridge of a known inkjet recording device, eject ink droplets, and attach the droplets to a recording medium such as paper to record an image. As the inkjet recording device, an inkjet recording device configured to be equipped with an electric distortion element capable of vibrating based on an electric signal and to be able to eject ink by the vibration of the electric distortion element is preferable. The recording medium is not particularly limited, and examples thereof include paper, cardboard, textile products, leather, sheets or films, plastics, glass, ceramics, metals and the like.

2. 2. Inkjet Recording Method The inkjet recording method according to the present embodiment is an inkjet recording method in which ink is ejected by an inkjet method to record an image on a recording medium, and the ink constitutes the ink set according to the above embodiment. It is characterized by being cyan ink, magenta ink and yellow ink.

The inkjet recording method according to the present embodiment can be performed using a conventionally known inkjet recording apparatus similar to the above.

Since the inkjet recording method according to the present embodiment is performed using the ink set according to the above embodiment, the inkjet recording method is excellent in robustness such as heat resistance and moisture resistance in a monochrome image.

3. 3. Examples Hereinafter, the present invention will be described in more detail 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 6 and pressure-filtered with a membrane filter having a pore size of 10 μm to obtain each ink composition. The numerical values in Table 6 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 Tables 6 to 8, the components described by the trade names are as follows.
Surfinol 104PG50 (trade name, manufactured by Air Products Japan Co., Ltd., acetylene glycol-based surfactant without alkylene oxide adduct of acetylene glycol having 10 carbon atoms in the main chain)
・ Surfinol MD-20 (trade name, manufactured by Air Products Japan Co., Ltd., acetylene glycol-based surfactant with HLB of 4 or less)
Orfin E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., a surfactant having an alkylene oxide adduct of acetylene glycol having 10 carbon atoms in the main chain).

Details of the dyes used in Table 6 are as follows.
-Magenta dye M1: The above-mentioned exemplary compound (2-20)
-Magenta dye M2: The above-mentioned exemplary compound (4)
-Magenta dye M3: The above-mentioned exemplary compound (M-23).
-Magenta dye M4: The above-mentioned exemplary compound (M-1-2)

Details of the dyes used in Table 7 are as follows.
Cyan dye C1: The following exemplary compound (1-5)
-Cyan dye C2: The above-mentioned exemplary compound (3-1)
-Cyan dye C3: C.I. I. Direct blue 199

一般式（１−５）中、
破線で表される環Ａ_１乃至Ａ_３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又は６員環の含窒素複素芳香環を表し、前記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及びｃの和は、平均値で１．００以上４．００未満である。

In the general formula (1-5),
_{Rings A 1 to} A ₃ represented by broken lines represent benzene rings or 6-membered nitrogen-containing heteroaromatic rings independently fused to porphyrazine rings, and the number of nitrogen-containing heteroaromatic rings is an average value. More than 0.00 and less than 3.00, the rest are benzene rings,
b has an average value of 0.00 or more and less than 3.90.
c has an average value of 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.

Details of the dyes used in Table 8 are as follows.
-Yellow dye Y1: The above-mentioned exemplary compound (Y-1)
-Yellow dye Y2: The above-mentioned exemplary compound (Y-2)
-Yellow dye Y3: C.I. I. Direct yellow 132
-Yellow dye Y4: C.I. I. Acid Yellow 1
-Yellow dye Y5: C.I. I. Acid Yellow 73

The exemplified compound (2-20) was synthesized as follows with reference to the method described in JP-A-2016-41801.

<Synthesis of Exemplified Compound (2-20)>

<Synthesis of intermediate (B)>
23.0 g of Intermediate (A) (synthesized by the method described in paragraph No. 0065 of page 17 of JP-A-2011-148973) 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 filtered crystals were dissolved in 500 mL of methanol, adjusted to pH 7 with a 28% sodium methoxide methanol solution, and the precipitated sodium sulfate was removed by filtration. The filtrate is concentrated using a rotary evaporator, and the obtained residue is purified by column chromatography (filler: Sephadex LH-20 (manufactured by Pharmacia), developing solvent: methanol) to obtain crystals of the intermediate (B). rice field. Yield 21.0 g, yield 68%, MS (m / z) = 793 ([M-2Na + H] ⁻ , 100%).

To 4 g of the obtained intermediate (B), 2.0 g of methanesulfonyl chloride was added, and then 8 mL of pyridine was slowly added dropwise, and the mixture was reacted at room temperature for 3 hours. The reaction solution was added to a large excess of ethyl acetate, and the precipitated crystals were filtered off. The obtained crystals were dissolved in 50 mL of water, adjusted to pH 7 with a dilute aqueous sodium hydroxide solution, and the obtained aqueous solution was purified by column chromatography (filler: Cefadex LH-20, developing solvent: water / methanol). Green glossy crystals of the exemplary compound (1-20) were obtained. Yield 3.0 g, yield 63%. MS (m / z) = 993 ([M-1] ⁻ , 100%). The maximum absorption wavelength of the absorption spectrum of the exemplified compound (2-20) in a dilute aqueous solution was 533 nm, and the molar extinction coefficient was 54000.

Exemplified compounds (4), (M-23) and (M-1-2) were synthesized with reference to the method described in JP-A-2016-29148. The exemplary compound (1-5) was synthesized with reference to the method described in JP2012-12230. The exemplary compound (3-1) was synthesized with reference to the method described in JP-A-2016-29148. Exemplified compounds (Y-1) and (Y-2) were synthesized with reference to the methods described in JP-A-2007-63520.

3.2. Evaluation test 3.2.1. Evaluation of monochrome image fastness (heat resistance) After filling the ink container of the ink continuous supply system (CISS) type inkjet printer (manufactured by Seiko Epson Corporation, model "EW-M660FT") with ink, a pattern is obtained under the following conditions. Was printed, and the obtained printed matter was dried at room temperature for 24 hours, and then the L value a value b value of the printed matter was measured. Then, after leaving the printed matter in the environment, the L value a value b value was measured again. Regarding the color difference before and after leaving, ΔE00 based on the CIE DE2000 color difference was calculated and evaluated according to the following criteria.
(Printing conditions)
Recording medium: Photo paper <gloss> manufactured by Seiko Epson Corporation
Print settings: Paper type = EPSON photo paper
(Others are the default settings)
Printing environment: 25 ° C, 40% RH
Print pattern: Gray patch (R, G, B) = (128, 128, 128)
Colorimeter: Spectrophotometer; X-Rite i1 (manufactured by X-Rite),
No light source filter, light source: D50, viewing angle 2 degrees Leaving conditions: 80 ° C, 20%, 30 days (evaluation criteria)
A: ΔE00 is 0.7 or more B: ΔE00 is more than 0.7 and 1.2 or less C: ΔE00 value is more than 1.2

3.2.2. Evaluation of Monochrome Image Fastness (Moisture Resistance) After filling the ink container of the above CISS type inkjet printer with ink, a pattern was printed under the following conditions. The obtained printed matter was dried at room temperature for 24 hours, left in an environment, and the bleeding of the printed matter was visually judged and evaluated according to the following criteria.
(Printing conditions)
Recording medium: Photo paper <gloss> manufactured by Seiko Epson Corporation
Print settings: Paper type = EPSON photo paper
(Others are the default settings)
Printing environment: 25 ° C, 40% RH
Print pattern: Solid pattern with 6-point outline characters Colorimeter: Spectrophotometer; X-Rite i1 (manufactured by X-Rite),
No light source filter, light source: D50, viewing angle 2 degrees Leaving conditions: 40 ° C, 85%, 30 days (evaluation criteria)
A: There is no bleeding and outline characters can be recognized.
B: Although there is some blurring, outline characters can be recognized.
C: There is bleeding, but outline characters are barely recognizable.

3.2.3. Evaluation of Gas Resistance After filling the ink container of the above CISS type inkjet printer with the ink of the example, a pattern was printed under the following conditions. The obtained printed matter was dried at room temperature for 24 hours, and then the OD value was measured. Then, after leaving the printed matter in the environment, the OD value was measured again. A series of procedures was performed according to JEITA CP-3901A, and the gray imbalance (CY, YY, MC) of the composite neutral patch was calculated and evaluated according to the following criteria.
(Printing conditions)
Recording medium: Photo paper <gloss> manufactured by Seiko Epson Corporation
Print resolution: 600 x 1200 dpi
Printing environment: 25 ° C, 40% RH
Print pattern: JEITA CP-3901A Life prediction chart Colorimeter: Spectrophotometer; X-Rite i1 (manufactured by X-Rite),
No light source filter, light source: D50, viewing angle 2 degrees Leaving condition: Ozone weather meter (trade name "OMS-L", manufactured by Suga Test Instruments Co., Ltd.) is used. Leave at 23 ° C. 50%, ozone concentration 5 ppm, for 40 hours.
(Evaluation criteria)
A: The gray imbalance of the composite neutral patch is within 10%.
B: The gray imbalance of the composite neutral patch is over 10% and within 15%.
C: The gray imbalance of the composite neutral patch is over 15%.

3.2.4. Evaluation of Light Resistance After filling the ink container of the above CISS type inkjet printer with the ink of the example, a pattern was printed under the following conditions. The obtained printed matter was dried at room temperature for 24 hours, and then the OD value was measured. Then, after leaving the printed matter in the environment, the OD value was measured again. A series of procedures was performed according to JEITA CP-3901A, and the gray imbalance (CY, YY, MC) of the composite neutral patch was calculated and evaluated according to the following criteria.
(Printing conditions)
Recording medium: Photo paper <gloss> manufactured by Seiko Epson Corporation
Print resolution: 600 x 1200 dpi
Printing environment: 25 ° C, 40% RH
Print pattern: JEITA CP-3901A Life prediction chart Colorimeter: Spectrophotometer; X-Rite i1 (manufactured by X-Rite),
No light source filter, light source: D50, viewing angle 2 degrees Leaving condition: xenon weather meter (trade name "X75L", manufactured by Suga Test Instruments Co., Ltd.) is used. Leave until 23 ° C 50%, irradiance 0.95 W / m ² , integrated illuminance 7665 klux · h (equivalent to 7 years).
(Evaluation criteria)
A: The gray imbalance of the composite neutral patch is within 10%.
B: The gray imbalance of the composite neutral patch is over 10% and within 15%.
C: The gray imbalance of the composite neutral patch is over 15%.

3.2.5. Evaluation of Color Development After filling the ink container of the above CISS type inkjet printer with the ink of the example, a pattern was printed under the following conditions. The obtained printed matter was dried at room temperature for 24 hours, and then the OD value was measured and evaluated according to the following criteria.
(Printing conditions)
Recording medium: Photo paper <gloss> manufactured by Seiko Epson Corporation
Print resolution: 600 x 1200 dpi
Printing environment: 25 ° C, 40% RH
Print pattern: Gray patch (R, G, B) = (128, 128, 128)
Colorimeter: Spectrophotometer; X-Rite i1 (manufactured by X-Rite),
(Evaluation criteria)
A: OD value 1.07 or more B: OD value 1.00 or more and less than 1.07 C: OD value less than 1.00

3.3. Evaluation Results The evaluation results are shown in Table 9.

As shown in Table 9, in each of the examples, the result was excellent in the robustness of the monochrome image. In particular, when each ink is a combination containing two kinds of dyes, gas resistance, light resistance, and color development tend to be further improved. This is because the dyes contained in each ink have high flatness, symmetry, and high association, so when composite gray is printed on a recording medium, they tend to stack (aggregate) at the molecular level with each other, and the monochrome image is robust. It is presumed that the sex is enhanced. For example, in the case of a yellow dye, the triazine skeleton portion has a high intramolecular association, and it is presumed that the action effect is higher than that of a general azo dye.

On the other hand, in the comparative example outside the scope of the present invention, the robustness was low. In Comparative Examples 1 to 3, the magenta ink did not contain a compound having a xanthene skeleton, resulting in inferior monochrome image fastness, and in Comparative Example 1, the gas resistance was also reduced. In Comparative Examples 4 and 5, since the cyan ink did not contain the porphyrazine-based compound represented by the general formula (1), the monochrome image fastness was inferior, and in Comparative Example 5, the gas resistance was also lowered. In Comparative Examples 6 to 8, since the yellow ink does not contain a compound having a dimeric disazo structure formed by binding via a triazine skeleton, the monochrome image fastness is also inferior, and in Comparative Examples 7 and 8, the light resistance is reduced. The sex also declined.

As shown above, the cyan ink contains a porphyrazine-based compound represented by the general formula (1) or a salt thereof, the magenta ink contains a compound having a xanthene skeleton or a salt thereof, and the yellow ink contains a compound having a xanthene skeleton or a salt thereof. In the case of containing a compound having a dimeric disazo structure formed by binding via a triazine skeleton or a salt thereof, the result was excellent in the fastness of the monochrome image. In addition, the results were excellent in gas resistance, light resistance, and color development.

The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. Further, the present invention includes a configuration having the same action and effect as the configuration described in the embodiment or a configuration capable of achieving the same object. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (9)

An ink set containing cyan ink, magenta ink, and yellow ink.
The cyan ink contains a porphyrazine-based compound represented by the following general formula (1) or a salt thereof.
The magenta ink contains a compound having a xanthene skeleton or a salt thereof,
An ink set in which the yellow ink contains a compound having a dimeric disazo structure formed by binding via a triazine skeleton or a salt thereof.

In general formula (1),
The rings A to D represented by the broken lines represent benzene rings or 6-membered nitrogen-containing heteroaromatic rings independently fused to porphyrazine rings, and the number of nitrogen-containing heteroaromatic rings is 0.00 on average. More than 3.00 or less, the rest are benzene rings,
E represents C2-C12 alkylene and represents
X has a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group and a di-C1-C4 alkylamino group as substituents. , Mono C6-C10 arylamino group, di C6
-Selected from the group consisting of C10 arylamino group, C1-C3 alkylcarbonylamino group, ureido group, C1-C6alkyl group, nitro group, cyano group, halogen atom, C1-C6alkylsulfonyl group, and C1-C6alkylthio group. It is a sulfoanilino group, a carboxyanilino group, a phosphonoanilino group, a sulfonaphthylamino group, a carboxynaphthylamino group or a phosphononaphthylamino group, which may have one or more substituents.
R is a hydrogen atom; a sulfo group; a carboxy group; a phosphate group; a sulfamoyl group; a carbamoyl group; a hydroxy group; a C1-C6 alkoxy group; an amino group; a mono C1-C6 alkylamino group; a diC1-C6 alkylamino group; a mono Represents an arylamino group; a diarylamino group; a C1-C3 alkylcarbonylamino group; a ureido group; a C1-C6 alkyl group; a nitro group; a cyano group; a halogen atom; a C1-C6 alkylsulfonyl group; or an alkylthio group;
Group F is phenylene group; or 6-membered nitrogen-containing heteroaromatic ring group; represent,
a represents an integer of 1 or more and 6 or less,
b has an average value of 0.00 or more and less than 3.90.
c has an average value of 0.10 or more and less than 4.00.
Moreover, the sum of b and c is 1.00 or more and less than 4.00 on average. In the porphyrazine-based compound represented by the general formula (1) or a salt thereof,
The nitrogen-containing heteroaromatic rings in the rings A to D are independently fused pyridine rings at the 2- and 3-positions or at the 3- and 4-positions; or pyrazine rings condensed at the 2- and 3-positions. ,
E is a linear C2-C4 alkylene,
X is a sulfo group, a carboxy group, a hydroxy group, a C1-C6 alkoxy group, an amino group, a mono-C1-C4 alkylamino group, a diC1-C4 alkylamino group, a C1-C3 alkylcarbonylamino group, and a nitro as substituents. It may have 0 to 2 substituents of 1 or 2 selected from the group consisting of groups, halogen atoms, C1-C6 alkylsulfonyl groups and alkylthio groups; sulfoanilino groups; sulfo groups as substituents. , A carboxyanilino group which may have 0 to 2 substituents of 1 or 2 selected from the group consisting of a carboxy group, a hydroxy group, and a sulfamoyl group; a phosphonoanilino group; or a sulfo as a substituent. A sulfonaphthylamino group which may have 0 to 2 substituents of 1 or 2 selected from a group and a hydroxy group;
R is a hydrogen atom; a, group F is phenylene group; a sulfo group; a carboxy group; C1-C6 alkoxy group; C1-C6 alkyl group; or a halogen atom, or, R is pyridyl group is a hydrogen atom; a ,
The ink set according to claim 1, wherein a is an integer of 1 or 2. In the porphyrazine-based compound represented by the general formula (1) or a salt thereof,
The nitrogen-containing heteroaromatic rings in the rings A to D are pyridine rings that are independently fused at the 2- and 3-positions, respectively.
E is ethylene,
X is a sulfoanilino group which may have 0 or 1 sulfo group as a substituent; or a sulfonaphthylamino group which has 2 sulfo groups as a substituent.
R is a hydrogen atom, a sulfo group, or a carboxy group,
Group F is phenylene group, or a pyridyl group R is a hydrogen atom,
a is an integer of 1
b is 0.00 or more and less than 3.90 on average,
c is an average value of 0.10 or more and less than 4.00,
The ink set according to claim 1 or 2, wherein the sum of b and c is 1.00 or more and less than 4.00 on average. The ink set according to any one of claims 1 to 3, wherein the compound having a xanthene skeleton is a compound represented by the following general formula (2).

In the general formula (2), 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 are independently substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or absent, respectively. Substituent 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 , Substituent or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylaminocarbonyl group, or substituted or unsubstituted alkyl Represents an arylaminocarbonyl group. 4. In the compound represented by the general formula (2) ^{, claim 4 in which the R 1} , R ³ , R ⁵ , R ⁶ , R ⁸ and R ¹⁰ each independently represent an alkyl group having 1 or more and 6 or less carbon atoms. The ink set described in. The ink set according to any one of claims 1 to 5, wherein the cyan ink contains a phthalocyanine compound represented by the following general formula (3).

In general formula (3),
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide, or a metal halide.
Z ₁ to Z ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group, each may further have a substituent. The sixth aspect of the present invention, wherein the compound represented by the general formula (3) contains a compound represented by the following general formula (3-1) and a compound represented by the following general formula (3-2). The described ink set.

In the general formula (3-1), R represents SO ₂ (CH ₂ ) ₃ SO ₃ Na.

In the general formula (3-2), any two of R represent SO ₂ (CH ₂ ) ₃ SO ₃ Li, and the remaining two represent SO ₂ (CH ₂ ) ₃ SO ₂ NHCH ₂ CH (OH) CH. Represents _3. The ink set according to any one of claims 1 to 7, wherein the magenta ink contains a compound represented by the following general formula (4).

It is an inkjet recording method in which ink is ejected by an inkjet method and an image is recorded on a recording medium.
The inkjet recording method, wherein the ink is cyan ink, magenta ink, and yellow ink constituting the ink set according to any one of claims 1 to 8.