JP5779494B2 - Coloring composition, inkjet recording ink, and inkjet recording method - Google Patents

Description

  The present invention relates to a coloring composition comprising a compound having a specific xanthene skeleton and a specific anthrapyridone compound, an ink for ink jet recording, and an ink jet recording method.

  As is well known, the ink jet recording method is a method of performing printing by causing a small droplet of ink to fly and adhere to a recording medium such as paper. This printing method is capable of printing high-resolution, high-quality images at high speed and easily with an inexpensive apparatus. In particular, in color printing, technical development has recently been carried out as an image forming method that can replace photographs. .

  When forming a color image using an inkjet recording method, it is common to use at least yellow ink, magenta ink, cyan ink, and black ink. Conventionally, water-based inks are mainly used for these ink-jet inks from the viewpoint of safety such as odor and fire hazard. These inks have physical properties such as viscosity and surface tension within an appropriate range, nozzle clogging, excellent storage stability, and a high density recording image, light resistance, ozone resistance, Properties such as excellent water resistance and moisture resistance are required.

  Many of these performances are satisfied by using water or a water-based ink containing a mixture of water and a water-soluble organic solvent as a main solvent, but color tone, vividness, light resistance, ozone resistance, water resistance Moisture resistance depends largely on the colorant, and various dyes have been studied in the past.

  Conventionally, as a magenta dye for inkjet, an acid dye having good color development and high water solubility, such as C.I. I. Acid Red 52, 249, 289, etc. are known, but when these dyes are used alone, the nozzle is not clogged due to its high water solubility, but the performance of ozone resistance, light resistance, and moisture resistance is high. Was very low.

  Patent Document 1 discloses C.I., a xanthene derivative. I. Acid Red 289 and C.I. I. A water-based ink for ink-jet recording containing a dye comprising a xanthene derivative having more sulfo groups than Acid Red 289 is described.

  Patent Documents 2 and 3 disclose that a specific compound having an andrapyridone skeleton provides a magenta dye having a good hue and fastness to light, ozone, and humidity.

  Patent Document 4 describes an ink in which a xanthene compound and an andrapyridone compound are used in combination.

British Patent No. 2134129 JP 2003-192930 A International Publication No. 04/104108 US Patent Application Publication No. 2011/0067598 Specification

However, the dye specifically described in Patent Document 1 is required to further improve ozone resistance, light resistance, and moisture resistance. Further, the dyes described in Patent Documents 2 and 3 have good fastness such as light resistance and ozone resistance, but the printing density is insufficient. That is, in either case, the fastness and the print density are not sufficiently compatible. Similarly, Patent Document 4 also requires further improvement in performance.
An object of this invention is to provide the coloring composition which is excellent in ozone resistance, light resistance, and moisture resistance, and excellent in the viewpoint of a printing density. Another object of the present invention is to provide an ink jet recording ink containing the coloring composition, and an ink jet recording method using the ink jet recording ink.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a coloring composition containing a compound having a xanthene skeleton having a specific number of sulfo groups introduced therein and a specific dye having an anthrapyridone skeleton is resistant to ozone and light. The present invention has been completed by finding that the image fastness such as property and moisture resistance and the performance relating to the print density are better than expected.

一般式（１）中、Ｄは下記一般式（２）で表される化合物からｎ個の水素原子を取り除いた残基を表し、ｎは４〜６の数を表す。Ｍは水素原子又はカウンターカチオンを表す。
Ｍはそれぞれ同じであっても異なっていてもよい。

一般式（２）中、Ｒ ^１０１ 、Ｒ ^１０２ 、及びＲ ^１０３ は各々独立に１価の置換基を表し、Ｒ ^１０４ 及びＲ ^１０５ は各々独立に水素原子又は１価の置換基を表し、ｎ１０１及びｎ１０２は各々独立に０〜５の数を表し、ｎ１０３は０〜４の数を表す。ｎ１０１、ｎ１０２及びｎ１０３がそれぞれ２以上の数を表す場合は、複数のＲ ^１０１ 、Ｒ ^１０２ 、及びＲ ^１０３ は同じであっても異なっていてもよい。

一般式（４）中、Ｒ _２１ 及びＲ _２２ は、各々独立に、水素原子、又は置換若しくは無置換のアルキル基を表す。
Ｙ _２１ 及びＹ _２２ は、各々独立に、塩素原子、ヒドロキシル基、置換若しくは無置換のアミノ基、アルコキシ基、置換若しくは無置換のフェノキシ基を表す。
Ｘは２価の連結基を表す。
Ｍ ^４ は水素原子又はカウンターカチオンを表す。Ｍ ^４ はそれぞれ同じであっても異なっていてもよい。

一般式（５）中、Ｒ _３１ は水素原子、又は置換若しくは無置換のアルキル基を表す。
Ｙ _３１ は、塩素原子、ヒドロキシル基、置換若しくは無置換のアミノ基、又はモルホリノ基を表す。
Ｍ ^５ は水素原子又はカウンターカチオンを表す。Ｍ ^５ はそれぞれ同じであっても異なっていてもよい。
Ｘ _３１ は下記一般式（５−１）で表される基を表す。

一般式（５−１）中、Ｒ _３２ 、Ｒ _３３ 、Ｒ _３４ 、Ｒ _３５ 、及びＲ _３６ は、各々独立に、水素原子、炭素数１〜８のアルキル基、又は−ＣＯＯＭ’（Ｍ’は水素原子又はカウンターカチオンを表す）を表す。ただし、Ｒ _３２ 、Ｒ _３３ 、Ｒ _３４ 、Ｒ _３５ 、及びＲ _３６ のうち少なくとも１つは炭素数１〜８のアルキル基、又は−ＣＯＯＭ’を表す。
＜２＞
前記一般式（１）におけるｎが４である、＜１＞に記載の着色組成物。
＜３＞
前記一般式（１）で表される化合物が、下記一般式（３）で表される化合物である、＜１＞又は＜２＞に記載の着色組成物。

一般式（３）中、Ｒ ^２０１ 、Ｒ ^２０２ 、及びＲ ^２０３ は各々独立に１価の置換基を表し、ｎ２０１及びｎ２０２は各々独立に０〜４の数を表し、ｎ２０３は０〜４の数を表す。ｎ２０１、ｎ２０２、及びｎ２０３がそれぞれ２以上の数を表す場合は、複数のＲ ^２０１ 、Ｒ ^２０２ 、及びＲ ^２０３ は同じであっても異なっていてもよい。Ｍは水素原子又はカウンターカチオンを表す。Ｍはそれぞれ同じであっても異なっていてもよい。
＜４＞
前記Ｒ ^１０１ 、Ｒ ^１０２ 、Ｒ ^１０３ 、Ｒ ^２０１ 、Ｒ ^２０２ 、及びＲ ^２０３ が、各々独立にアルキル基又はアシルアミノ基を表す、＜１＞〜＜３＞のいずれか一項に記載の着色組成物。
＜５＞
前記Ｒ ^１０１ 、Ｒ ^１０２ 、Ｒ ^１０３ 、Ｒ ^２０１ 、Ｒ ^２０２ 、及びＲ ^２０３ が、各々独立に炭素数１〜６のアルキル基を表す、＜１＞〜＜４＞のいずれか一項に記載の着色組成物。
＜６＞
前記ｎ１０１、ｎ１０２、ｎ２０１、及びｎ２０２が、各々独立に２〜４の数を表す、＜１＞〜＜５＞のいずれか一項に記載の着色組成物。
＜７＞
前記ｎ１０３、及びｎ２０３が、０を表す、＜１＞〜＜６＞のいずれか一項に記載の着色組成物。
＜８＞
前記Ｍが、リチウムイオン、ナトリウムイオン、又はカリウムイオンである、＜１＞〜＜７＞のいずれか一項に記載の着色組成物。
＜９＞
前記Ｒ _２１ 、Ｒ _２２ 、及びＲ _３１ が、各々独立に、水素原子又は無置換のアルキル基である、＜１＞〜＜８＞のいずれか一項に記載の着色組成物。
＜１０＞
前記Ｙ _２１ 、Ｙ _２２ 、及びＹ _３１ が、各々独立に、塩素原子、ヒドロキシル基又は無置換のアミノ基である＜１＞〜＜９＞のいずれか一項に記載の着色組成物。
＜１１＞
一般式（１）で表される化合物の含有率が１〜２０質量％である＜１＞〜＜１０＞のいずれか一項に記載の着色組成物。
＜１２＞
一般式（４）で表される化合物、及び一般式（５）で表される化合物の合計の含有率が１〜２０質量％である＜１＞〜＜１１＞のいずれか一項に記載の着色組成物。
＜１３＞
一般式（１）で表される化合物の含有量と、一般式（４）で表される化合物及び一般式（５）で表される化合物の合計の含有量との質量比が９／１〜１／９である＜１＞〜＜１２＞のいずれか一項に記載の着色組成物。
＜１４＞
＜１＞〜＜１３＞のいずれか一項に記載の着色組成物を含有するインクジェット記録用インク。
＜１５＞
＜１＞〜＜１３＞のいずれか一項に記載の着色組成物、又は請求項１４に記載のインクジェット記録用インクを用いて、画像形成するインクジェット記録方法。
本発明は、前記＜１＞〜＜１５＞に係る発明であるが、以下、それ以外の事項についても参考のため記載している。 That is, the present invention is as follows.
<1>
A compound represented by the following general formula (1):
At least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5);
A coloring composition comprising:

In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 4-6. M represents a hydrogen atom or a counter cation.
M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

In general formula (4), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₂₁ and Y ₂₂ each independently represent a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, an alkoxy group, or a substituted or unsubstituted phenoxy group.
X represents a divalent linking group.
M ⁴ represents a hydrogen atom or a counter cation. M ⁴ may be the same or different from each other.

In the general formula (5), R ₃₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₃₁ represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.
M ⁵ represents a hydrogen atom or a counter cation. M ⁵ may be the same or different from each other.
X ₃₁ represents a group represented by the following general formula (5-1).

In General Formula (5-1), R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —COOM ′ (M ′ is Represents a hydrogen atom or a counter cation). However, at least one of R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represents an alkyl group having 1 to 8 carbon atoms or —COOM ′.
<2>
The coloring composition as described in <1> whose n in the said General formula (1) is 4.
<3>
The colored composition according to <1> or <2>, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different.
<4>
The colored composition according to any one of <1> to <3>, wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represents an alkyl group or an acylamino group. .
<5>
The R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an alkyl group having 1 to 6 carbon atoms, according to any one of <1> to <4>. Coloring composition.
<6>
The colored composition according to any one of <1> to <5>, wherein n101, n102, n201, and n202 each independently represent a number of 2 to 4.
<7>
The colored composition according to any one of <1> to <6>, wherein n103 and n203 represent 0.
<8>
The coloring composition as described in any one of <1>-<7> whose said M is a lithium ion, a sodium ion, or a potassium ion.
<9>
The colored composition according to any one of <1> to <8>, wherein R ₂₁ , R ₂₂ , and R ₃₁ are each independently a hydrogen atom or an unsubstituted alkyl group.
<10>
The colored composition according to any one of <1> to <9>, wherein Y ₂₁ , Y ₂₂ , and Y ₃₁ are each independently a chlorine atom, a hydroxyl group, or an unsubstituted amino group.
<11>
The coloring composition as described in any one of <1>-<10> whose content rate of the compound represented by General formula (1) is 1-20 mass%.
<12>
<1>-<11> as described in any one of <1>-<11> whose total content rate of the compound represented by General formula (4) and the compound represented by General formula (5) is 1-20 mass%. Coloring composition.
<13>
The mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) is 9/1 to The coloring composition as described in any one of <1>-<12> which is 1/9.
<14>
<1>-<13> The ink for inkjet recording containing the coloring composition as described in any one of <13>.
<15>
An inkjet recording method for forming an image using the colored composition according to any one of <1> to <13> or the inkjet recording ink according to claim 14.
The present invention is the invention according to the above <1> to <15>, but other matters are described below for reference.

[1]
A compound represented by the following general formula (1):
At least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5);
A coloring composition comprising:

  In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 3-6. M represents a hydrogen atom or a counter cation. M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

In general formula (4), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₂₁ and Y ₂₂ each independently represent a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, an alkoxy group, or a substituted or unsubstituted phenoxy group.
X represents a divalent linking group.
M ⁴ represents a hydrogen atom or a counter cation. M ⁴ may be the same or different from each other.

In the general formula (5), R ₃₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₃₁ represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.
M ⁵ represents a hydrogen atom or a counter cation. M ⁵ may be the same or different from each other.
X ₃₁ represents a group represented by the following general formula (5-1).

In General Formula (5-1), R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —COOM ′ (M ′ is Represents a hydrogen atom or a counter cation). However, at least one of R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represents an alkyl group having 1 to 8 carbon atoms or —COOM ′.
[2]
The coloring composition according to [1], wherein n in the general formula (1) is 4.
[3]
The coloring composition according to [1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different.
[4]
The colored composition according to any one of [1] to [3], wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represents an alkyl group or an acylamino group. object.
[5]
Wherein ^{R 101, R 102, R 103} , R 201, R 202, and ^{R 203} are each independently represents an alkyl group having 1 to 6 carbon atoms, according to any one of the above [1] to [4] Coloring composition.
[6]
The colored composition according to any one of [1] to [5], wherein n101, n102, n201, and n202 each independently represent a number of 2 to 4.
[7]
The colored composition according to any one of [1] to [6], wherein n103 and n203 represent 0.
[8]
The colored composition according to any one of [1] to [7], wherein M is lithium ion, sodium ion, or potassium ion.
[9]
The colored composition according to any one of [1] to [8], wherein R ₂₁ , R ₂₂ , and R ₃₁ are each independently a hydrogen atom or an unsubstituted alkyl group.
[10]
The colored composition according to any one of [1] to [9], wherein Y ₂₁ , Y ₂₂ , and Y ₃₁ are each independently a chlorine atom, a hydroxyl group, or an unsubstituted amino group.
[11]
The coloring composition as described in any one of said [1]-[10] whose content rate of the compound represented by General formula (1) is 1-20 mass%.
[12]
The total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) is 1 to 20% by mass, according to any one of the above [1] to [11]. Coloring composition.
[13]
The mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) is 9/1 to The coloring composition according to any one of [1] to [12], which is 1/9.
[14]
Ink for inkjet recording containing the coloring composition as described in any one of said [1]-[13].
[15]
An inkjet recording method for forming an image using the colored composition according to any one of [1] to [13] or the inkjet recording ink according to [14].

  According to the present invention, there is provided a coloring composition that sufficiently satisfies both image fastness such as ozone resistance, light resistance and moisture resistance and a good print density. Also provided are an ink jet recording ink containing the coloring composition and an ink jet recording method using the ink jet recording ink. The colored composition of the present invention is particularly useful as a magenta ink.

FIG. 1 is a diagram showing a ¹ H NMR spectrum of compound (1A), which is an example of the compound represented by general formula (1) in the present invention, in deuterated dimethyl sulfoxide.

Hereinafter, the present invention will be described in detail.
First, in the present invention, the substituent group A is defined.

(Substituent group A)
Halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, Job aryloxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, an ionic hydrophilic group mentioned as an example. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

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

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

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

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

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

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, 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 a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

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

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

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

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

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

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

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

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

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

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

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

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

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

The alkyl or arylsulfonylamino group is preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

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

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

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

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

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

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

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

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

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

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

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

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

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

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

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

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

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

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

  The colored composition of the present invention comprises a specific compound having a xanthene skeleton represented by general formula (1) or a salt thereof, a specific anthrapyridone compound represented by general formula (4) or general formula (5), or Including those salts.

[Compound represented by the general formula (1)]
The coloring composition of the present invention contains a compound represented by the following general formula (1).

  In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 3-6. M represents a hydrogen atom or a counter cation. M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

  The compound represented by the general formula (1) is a xanthene dye in which 3 to 6 hydrogen atoms are substituted with a sulfo group in the compound represented by the general formula (2), and is represented by the general formula (4) described later. In combination with at least one selected from the group consisting of the compound represented by formula (5) and the compound represented by the general formula (5), interaction (deactivation due to intermolecular energy transfer of excitation energy and penetration in the printing medium) It is considered that a coloring composition can be obtained that exhibits synergistic effects due to the control of the property, and is extremely excellent in ozone resistance, light resistance, moisture resistance, and printing density.

  In general formula (1), n represents the number of 3-6, 4-6 are preferable on a synthetic | combination and an ozone-resistant viewpoint, 4 or 5 is more preferable, and 4 is still more preferable.

In General Formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represent a monovalent substituent.
Examples of the monovalent substituent represented by R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ include a substituent selected from the substituent group A. From the viewpoints of availability of raw materials and ease of synthesis, a halogen atom, aryl Group, alkoxy group, alkyl group and acylamino group are preferred, alkyl group and acylamino group are more preferred, and alkyl group is still more preferred.

When R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ represent an alkyl group, from the viewpoint of availability of raw materials, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is preferable. More preferred. Moreover, it is preferable that it is a linear or branched alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group, and a methyl group, an ethyl group, or an i-propyl group is preferable, and a methyl group Or an ethyl group is more preferable, and a methyl group is still more preferable.
The alkyl group may have a substituent, and examples of the substituent include a halogen atom and a hydroxyl group.
The alkyl group is preferably an unsubstituted alkyl group.

When R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ represent an acylamino group, the acyl group in the acylamino group is preferably an aliphatic acyl group from the viewpoint of availability of raw materials and color developability, and has 2 to 6 carbon atoms. More preferably, it is an aliphatic acyl group. Specific examples include an acetylamino group, a propionylamino group, a butyrylamino group, and the like, and an acetylamino group is particularly preferable.
The acylamino group is preferably a monoacylamino group.

In the general formula (2), R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent.
When R ¹⁰⁴ and R ¹⁰⁵ represent a monovalent substituent, examples of the monovalent substituent include a substituent selected from the substituent group A, and a substituted or unsubstituted alkyl group is preferable. The alkyl group is more preferable.
From the viewpoints of absorption characteristics and ozone resistance, R ¹⁰⁴ and R ¹⁰⁵ are preferably hydrogen atoms.

In general formula (2), n101 and n102 each independently represents a number of 0 to 5. From the viewpoint of availability of raw materials and ease of synthesis, n101 and n102 are preferably 1 to 5, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 2 or 3.
n101, and if n102 represents the number of 2 or more, respectively, a plurality of ^{R 101,} and ^{R 102} may be different even in the same.

In general formula (2), n103 represents the number of 0-4. From the viewpoint of availability of raw materials, n103 is preferably a number of 0 to 3, more preferably a number of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
If n103 represents the number of 2 or more, plural R ¹⁰³ may be different even in the same.

In the general formula (1), M represents a hydrogen atom or a counter cation. M may be the same or different.
In the general formula (1), when M is a hydrogen atom, it is in the form of a free acid, and when M is a counter cation, it is in the form of a salt.
Examples of counter cations that form salts include monovalent counter cations, and alkali metal ions, ammonium ions, organic cations, and the like are preferable.
Examples of the organic cation include tetramethylammonium ion, tetramethylguanidinium ion, and tetramethylphosphonium.
From the viewpoint of the availability of raw materials, the water solubility of dyes, and the suppression of gloss generation when creating secondary colors with other dyes when used as inkjet inks, alkali metal ions are preferred, lithium ions, sodium ions, Potassium ions are more preferred. In particular, sodium ion is preferable because it is inexpensive.
In the present invention, from the viewpoint of ease of synthesis (easy handling as a dye powder), the compound represented by the general formula (1) is preferably in the form of a salt, such as a lithium salt, a sodium salt, Or it is more preferable that it is a potassium salt, and it is still more preferable that it is a sodium salt.
In the general formula (1), M may be the same or different. That is, the compound represented by the general formula (1) is in the form of a salt when all the sulfo groups are in the form of a salt and when some of the sulfo groups are in the form of a free acid. This includes the case where a part of the sulfo group is a salt. Moreover, the counter cation forming the salt may be one kind or plural kinds.
In the present invention, from the viewpoint of ease of synthesis (easy handling as a dye powder), the compound represented by the general formula (1) is preferably in the form of a salt, and all sulfo groups are salts. Is more preferable.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (3).
The compound represented by the following general formula (3) can inhibit the attack of oxidizing gas (oxygen or ozone) on the nitrogen atom due to the steric hindrance of the sulfo group introduced adjacent to the nitrogen atom. It is considered particularly excellent in terms of ozone resistance and light resistance.

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different.

Specific examples and preferred ranges of R ²⁰¹ , R ²⁰² , R ²⁰³ , n203, and M in the general formula (3) are specific examples of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , n103, and M in the general formula (2) and This is the same as the preferred range.
N201 and n202 in the general formula (3) each independently represent a number of 0 to 4, and from the viewpoint of availability of raw materials and ease of synthesis, a number of 1 to 4 is preferable, and a number of 2 to 4 is preferable. 2 or 3 is more preferable.

  Although the specific example of a compound represented by General formula (1) below is given, it is not necessarily limited to these. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ac represents an acetyl group.

A method for synthesizing the compound represented by the general formula (1) will be described.
After synthesizing a xanthene dye according to a conventionally known method for synthesizing xanthene dyes, or using a commercially available xanthene dye and chlorosulfonylating with a combination of chlorosulfonic acid / phosphorus oxychloride, followed by alkaline hydrolysis Can be synthesized (see scheme below). Details will be described in Examples described later.

[Compound represented by formula (4)]

In general formula (4), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₂₁ and Y ₂₂ each independently represent a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, an alkoxy group, or a substituted or unsubstituted phenoxy group.
X represents a divalent linking group.
M ⁴ represents a hydrogen atom or a counter cation. M ⁴ may be the same or different from each other.

In general formula (4), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.

When R ₂₁ and R ₂₂ represent an alkyl group, the alkyl group may be linear, branched, or cyclic (cycloalkyl group), preferably an alkyl group having 1 to 10 carbon atoms, Preferably it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Most preferably, it is a C1-C4 alkyl group.
When the alkyl group is a cyclic alkyl group, a cyclohexyl group is preferable.
The alkyl group is more preferably a linear or branched alkyl group.
Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, cyclohexyl group and the like.

When R ₂₁ and R ₂₂ represent an alkyl group, the alkyl group may have a substituent. The substituent is preferably a hydroxyl group, a cyano group, or an amino group substituted with an alkyl group.
When the hydroxyl group or cyano group is substituted, the alkyl group is most preferably an ethyl group.
Examples of the amino group substituted with the alkyl group include a monoalkylamino group and a dialkylamino group, and the alkyl group is preferably linear or branched. Preferably, it is a mono- or dialkylamino group substituted by an alkyl group having 1 to 8 carbon atoms, more preferably a mono- or dialkylamino group substituted by an alkyl group having 1 to 6 carbon atoms, still more preferably 1 to 1 carbon atom. 4 is a mono or dialkylamino group substituted with an alkyl group, and particularly preferably a mono or dialkylamino group substituted with a methyl group or an ethyl group.

R ₂₁ and R ₂₂ are preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group, from the viewpoint of availability of raw materials. preferable.

In the general formula (4), Y ₂₁ and Y ₂₂ each independently represent a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, an alkoxy group, a substituted or unsubstituted phenoxy group.

When Y ₂₁ and Y ₂₂ represent an amino group, the amino group may have a substituent.
As the substituent, an alkyl group or an aryl group is preferable.

When Y ₂₁ and Y ₂₂ represent an amino group having an alkyl group as a substituent (alkylamino group), it may be a monoalkylamino group or a dialkylamino group.
The alkyl group may be linear, branched or cyclic (cycloalkyl group).
When the alkyl group is a linear or branched alkyl group, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a butyl group, and a 2-ethylhexyl group.
When the alkyl group is a linear or branched alkyl group, the alkyl group may further have a substituent. Examples of the further substituent include an alkylamino group, an aryl group, a sulfo group, a carboxyl group, and a hydroxyl group. Groups are preferred. When the alkyl group has a further substituent, it is an alkyl group having a substituent selected from the group consisting of a sulfo group, a carboxyl group, and a hydroxyl group, or an alkyl group having an aryl group (aralkyl group). Or an alkyl group having an alkylamino group.

The alkyl group having a substituent selected from the group consisting of a sulfo group, a carboxyl group, and a hydroxyl group is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Groups and the like.
Specific examples of the mono- or dialkylamino group having a sulfo group or a carboxyl group include, for example, 2-sulfoethylamino group, carboxymethylamino group, 2-carboxyethylamino group, 1-carboxyethylamino group, 1,2- Examples thereof include a dicarboxyethylamino group and a di (carboxymethyl) amino group.
Specific examples of the mono- or dialkylamino group having a hydroxyl group include a hydroxyethylamino group and a dihydroxyethylamino group.

  The amino group having an aralkyl group is preferably an amino group having a C 1-6 alkyl group substituted by a phenyl group, and examples thereof include a benzylamino group, a phenethylamino group, and a phenylpropylamino group.

Alkylamino group for the further substituents may dialkylamino group with a monoalkylamino group, specific examples and preferred ranges of the alkyl amino group is the same as the alkylamino group as the Y ₂₁ and Y ₂₂ .

When Y ₂₁ and Y ₂₂ represent an amino group having a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms, and examples thereof include a cyclohexyl group and a cyclopentyl group.

When Y ₂₁ and Y ₂₂ represent an amino group having an aryl group as a substituent (arylamino group), an amino group substituted with a phenyl group or a naphthyl group is preferable.

  The amino group substituted with a phenyl group is preferably an anilino group. In the anilino group, in addition to the unsubstituted anilino group, at least one substituent selected from the group consisting of a sulfo group and a carboxyl group may be further substituted on the benzene ring. For example, 2,5-disulfoanilino Group, 3-sulfoanilino group, 2-sulfoanilino group, 4-sulfoanilino group, 2-carboxy-4-sulfoanilino group, 2-carboxy-5-sulfoanilino group and the like.

  In addition to the unsubstituted naphthylamino group, the naphthyl group-substituted amino group (naphthylamino group) may be further substituted with a naphthyl group, such as 3,6,8-trisulfo-1-naphthyl. Examples include an amino group, 4,6,8-trisulfo-2-naphthylamino group, 3,6,8-trisulfo-2-naphthylamino group, 4,8-disulfo-2-naphthylamino group, and the like.

When Y ₂₁ and Y ₂₂ represent an alkoxy group, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a butoxy group.

When Y ₂₁ and Y ₂₂ represent a phenoxy group, the phenoxy group may be an unsubstituted phenoxy group or a phenoxy group having a substituent. The substituent is preferably at least one substituent selected from the group consisting of a sulfo group, a carboxy group, an acetylamino group, an amino group, and a hydroxyl group. Examples of the phenoxy group substituted with a substituent selected from the group consisting of a sulfo group, a carboxy group, an acetylamino group, an amino group, and a hydroxyl group include a 4-sulfophenoxy group, a 4-carboxyphenoxy group, 4- Examples include acetylamino-phenoxy group, 4-aminophenoxy group, 4-hydroxyphenoxy group and the like.

Y ₂₁ and Y ₂₂ are preferably a chlorine atom, a hydroxyl group, or an unsubstituted amino group from the viewpoint of moisture resistance.

In general formula (4), X represents a divalent linking group. The divalent linking group has a nitrogen atom or an oxygen atom at both ends of the hydrocarbon residue having 1 to 20 carbon atoms which may contain a nitrogen atom, an oxygen atom or a sulfur atom, A divalent group having an oxygen atom as a bond, specifically,
_{-N (H) m (-A-)} n N (H) m -, or -O-A-O-
(In the formula, A is a divalent hydrocarbon residue having 1 to 20 carbon atoms and may contain a nitrogen atom, an oxygen atom or a sulfur atom, n is 1 or 2, m is 1 or 0, and n M is 1 when n is 1, and m is 0 when n is 2).
Examples of the divalent hydrocarbon residue having 1 to 20 carbon atoms of A include, for example, 1 to 2 carbon atoms having 1 to 2 hetero atoms (for example, nitrogen atom, oxygen atom, sulfur atom and the like). A divalent aliphatic group, a divalent aromatic group having 3 to 10 carbon atoms, preferably 5 to 10 carbon atoms, which may contain 1 to 3 hetero atoms (for example, nitrogen atom, oxygen atom, sulfur atom and the like) and Examples thereof include a divalent group formed by combining the aliphatic group and the aromatic group. These groups may have a substituent (in the case of a sulfo group, a carboxyl group, an amino group, an aromatic group, etc., an alkyl group having 1 to 10 carbon atoms).

Examples of the aliphatic group include alkyl groups having 1 to 10 carbon atoms such as methylene, dimethylene (ethylene), trimethylene (propylene), 2-methyltrimethylene (2-methylpropylene), tetramethylene (butylene), and hexamethylene. (Poly) methylene optionally substituted with 1 to 6 carbon atoms, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3- C5-C7 cycloalkylene such as diyl, cyclohexane-1,4-diyl, cycloheptane-diyl, methylenecyclohexane-1,4-diylmethylene (—CH ₂ —C ₆ H ₁₀ —CH ₂ —), methylene dicyclohexane - diyl _{(-C 6 H 10 -CH 2 -C} 6 H 10 -), methylenebis (methylcarbamoyl Cyclohexane - _{diyl) {- C 6 H 10 (} CH 3) -CH 2 -C 6 H 10 (CH 3) -}, cyclohexane - diyl - dimethylene _{(-CH 2 -C 6 H 10 -CH} 2 -) , such as An aliphatic group consisting of an alkylene having 1 to 10 carbon atoms and an aliphatic ring having 5 to 7 carbon atoms (which may be substituted with an alkyl having 1 to 10 carbon atoms), methyleneoxymethylene (—CH ₂ —O—CH); _2- ), bis (dimethylene) amino (—C ₂ H ₄ —NH—C ₂ H ₄ —), methylenethiomethylene (—CH ₂ —S—CH ₂ —), oxydicyclohexane-diyl (—C ₆ H) _{10 -O-C 6 H 10 -} ) and aliphatic group of 1 to 7 carbon atoms can be mentioned including the hetero atom, such as.
Examples of the divalent aromatic group include aromatic groups having 6 to 10 carbon atoms such as phenylene (—C ₆ H ₄ —) and naphthylene (—C ₁₀ H ₆ —).
Examples of the divalent group formed by combining the aliphatic group and the aromatic group include xylylene (—CH ₂ —C ₆ H ₄ —CH ₂ —).
More preferable examples of A include dimethylene, hexamethylene, 1,3-xylylene, methylenedicyclohexane-4,1-diyl, methylenebis (2-methylcyclohexane-4,1-diyl), cyclohexane-1,3. -Diyl-dimethylene.

Examples of the divalent linking group X include a 1,2-diaminoethylene group (—NH—CH ₂ CH ₂ —NH—), a 1,4-diaminobutylene group (—NH—C ₄ H ₈ —NH—), Diaminoalkylene groups such as 1,6-diaminohexylene group (—NH—C ₆ H ₁₂ —NH—), 1,4-piperazinediyl group (—NC ₄ H ₈ N—), 1,4-diaminophenylene group _{(-NH-C 6 H 4 -p} -NH -), 1,3- diamino-phenylene group _{(-NH-C 6 H 4 -m} -NH-) diamino phenylene group such as, 4-Suruho 1,3-diamino phenylene group _{{-NH-C 6 H 4 (} p-SO 3 H) -m-NH -}, 5- Karubokishi 1,3-diamino-phenylene group substituted diamino phenylene group such as 1,3-diamino-xylylene group ( _-NH-CH 2 _-C 6 H _{-M-CH 2 -NH -),} 1,4- diamino-xylylene group _{(-NH-CH 2 -C 6 H} 4 -p-CH 2 -NH -), 4,4'- diamino-2-sulfo - diphenylamino group _{{-NH-C 6 H 4 (} m-SO 3 H) -NH-C 6 H 4 -p-NH -}, 4,4'- diaminodicyclohexylmethane group _{(-NH-C 6 H 10} - _{4-CH 2 -C 6 H 10} -4'-NH -), 4,4'- diamino-3,3'-dimethyl-dicyclohexylmethane group _{{-NH-C 6 H 10 (} 3-CH 3) -4- _{CH 2 -C 6 H 10 (3'} -CH 3) -4'NH -}, 1,3- bis (aminomethyl) cyclohexane group _{(-NH-CH 2 -C 6 H} 10 -3-CH 2 -NH -), dioxyethylene group _{(-O-CH 2 CH 2 -O} -), 1,4- Jiokishibu Len group _{(-O-C 4 H 8 -O} -), 2,2'- dioxy ether group _{(-O-CH 2 CH 2 -O} -CH 2 CH 2 -O-) dioxy substituted alkylene group such as 1,4-dioxyphenylene group (—O—C ₆ H ₄ —p—O—), 1,3-dioxyphenylene group (—O—C ₆ H ₄ —m—O—), 4,4 '-Dioxydiphenyl ether group (—O—C ₆ H ₄ —p—O—C ₆ H ₄ —p—O—), 4,4′-dioxyphenylene thioether group (—O—C ₆ H ₄ —p _{-S-C 6 H 4 -p-} O -), 2,5- and 2,6-norbornanedicarboxylic amino group, 1,4-oxymethyl-cyclohexylene group _{(-O-CH 2 -C 6 H} 10 -4 -CH ₂ -O-), and the like.
In the formula —N (H) _m (—A—) _n N (H) _m —, when n is 2 and m is 0, the group is 1,4-piperazinediyl (—NC _4). H ₈ N—) and the like.

  X is a diaminoethylene group, 1,4-piperazinediyl group, 1,3-diaminoxylylene group, 4,4'-diaminodicyclohexylmethane group, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane group 1,3-bis (aminomethyl) cyclohexane group is preferable.

In the general formula (4), M ⁴ represents a hydrogen atom or a counter cation. M ⁴ may be the same or different from each other.
In the general formula (4), when M ⁴ is a hydrogen atom, it is in the form of a free acid, and when M ⁴ is a counter cation, it is in the form of a salt.
Examples of counter cations that form salts include monovalent counter cations, and alkali metal ions, ammonium ions, organic cations, and the like are preferable.
Examples of the organic cation include a cation obtained by adding a hydrogen ion to an alkylamine or alkanolamine. Examples of the alkylamine include trimethylamine and triethylamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.
From the viewpoint of solubility, alkali metal ions are preferable, and lithium ions, sodium ions, and potassium ions are more preferable. In particular, sodium ions are preferred from the viewpoint of inexpensive production.
In the general formula (4), M ⁴ may be the same or different. That is, the compound represented by the general formula (4) is in the form of a salt when all the sulfo groups are in the form of a salt and when some of the sulfo groups are in the form of a free acid. This includes the case where a part of the sulfo group is a salt. Moreover, the counter cation forming the salt may be one kind or plural kinds.
The group other than the sulfo group that can be in the form of a salt (for example, a carboxyl group) is the same as described above.

Specific examples of the anthrapyridone compound represented by the general formula (4) are shown in Table 1. In Table 1, diaminoethylene means a 1,2-diaminoethylene group (—NH—CH ₂ CH ₂ —NH—). Ph represents a phenyl group, for example, Ph0 represents a phenoxy group, NHPh represents an anilino group, and so on. NHPh (p-SO ₃ H) represents a 4-sulfoanilino group (p-SO ₃ H represents that the sulfonic acid group is in the para position of the phenyl group), and NHPh (COOH) 2 (3,5) represents 3,5 -Dicarboxyanilino group {Ph (COOH) 2 (3,5) indicates that a carboxyl group is substituted at the 3-position and 5-position of the phenyl group}, and other groups are also described in the same manner. . Naphthyl represents a naphthyl group, NH-2naphthyl (SO3H) 3 (3,6,8) represents 3,6,8-trisulfo-2naphthylamino, and NH (cyclohexyl) represents cyclohexylamino. In the following specific examples, the sulfo group may be in a salt state.

A method for synthesizing the compound represented by the general formula (4) will be described.
In the compound of the general formula (4), for example, in order to obtain a compound having amino groups at both ends in X, a compound of the following formula (4-6) (wherein R ₂₁ represents the same meaning as above) 2 mol Is a primary condensate obtained by reacting 2,4,6-trichloro-S-triazine (cyanuric chloride) 2 to 2.4 mol in water with pH 3 to 7, 5 to 35 ° C. for 2 to 8 hours. To a compound of the formula (4-7) (wherein R ₂₁ represents the same meaning as above), 1 mol of the diamino compound of the following formula (4-8) is added at pH 4 to 10, 5 to 90 ° C., 10 minutes to By reacting for 5 hours, the compound of the formula (4-9) wherein Y is a chlorine atom and both ends of the bridging group X are amino groups (wherein R ₂₁ , R ₂₂ , m, n and A are the same as above) Is obtained as a secondary condensate.

HN (H) _m (-A-) _n N (H) _m H (4-8)

  In the formula, A is a linking group, for example, a divalent hydrocarbon residue having 1 to 20 carbon atoms, and may contain a nitrogen atom, an oxygen atom or a sulfur atom, n is 1 or 2, and m is 1 or 0 indicates that when n is 1, m indicates 1, and when n is 2, m indicates 0. Preferred examples of A include (poly) methylene having 1 to 6 carbon atoms, optionally substituted phenylene, xylylene, methylenedicyclohexane-diyl, methylenebis (methylcyclohexane-diyl), cyclohexane-diyl-dimethylene. And more preferably dimethylene, hexamethylene, 1,3-xylylene, methylenedicyclohexane-4,1-diyl, methylenebis (2-methylcyclohexane) -4,1-diyl, cyclohexane-1,3-diyl-dimethylene. Is mentioned.

However, when a compound represented by HN (-A-) ₂ NH (n = 2, m = 0 in formula (4-8)) such as piperidine in the above formula (4-8) is used, (4-9) in -NH-a-NH- instead -N of _(-A-) 2 N-a is compound. Then, it is hydrolyzed at pH 9-12, 70-90 ° C., 1-5 hours, or alcohol, such as ammonia, corresponding amines, phenols, naphthols or methanol, at pH 8-10, 90-100 ° C., By reacting for 3 to 8 hours, a compound of the formula (4-10) in which Y is not a chlorine atom is obtained as a tertiary condensate.

In addition, when a compound represented by HN (—A—) ₂ NH is used in the above formula (4-8), —N (instead of —NH—A—NH— in formula (4-10) is used. A compound which is -A-) ₂ N- is obtained.
The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above. Although many specific examples of the anthrapyridone compound represented by the above formula (4-10) of the present invention are contained in Table 1, preferred compounds in the present invention, including the compounds shown in Table 1, are listed below. It is shown in 2. In the following specific examples, the sulfo group may be in a salt state.

  By using a glycol compound represented by the following formula HO-A-OH (wherein A is the same as above) instead of the diamino compound of the formula (4-8), a condensation reaction is performed by a conventional method. Then, a compound in which the bridging group —NH—A—NH— in the above formula (4-9) is replaced by —O—A—O— is obtained, and then treated in the same manner as above to obtain a compound of the formula (4-10) In which the bridging group —NHA—NH— in place of —O—A—O— is obtained.

  The compound thus obtained exists in the form of the free acid or in the form of its salt. In the present invention, the free acid or a salt thereof can be used as an alkali metal salt, alkaline earth metal salt, alkylamine salt, alkanolamine salt or ammonium salt. Preferably, alkali metal salts such as sodium salt, potassium salt and lithium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, alkanolamine salt such as triisopropanolamine salt, ammonium Salt. As a method for preparing the salt, for example, sodium salt is added to the reaction solution of the tertiary condensate obtained above, salted out and filtered to obtain a sodium salt as a wet cake, and the wet cake is dissolved again in water. If crystals obtained by adding hydrochloric acid to adjust the pH to 1 to 2 are filtered, they can be obtained in the form of a free acid (or a part of it as a sodium salt). Furthermore, while the wet cake in the form of the free acid is stirred with water, for example, potassium hydroxide, lithium hydroxide, or aqueous ammonia is added to make it alkaline, thereby obtaining potassium salt, lithium salt, and ammonium salt, respectively. . In addition, the anthrapyridone compound of Formula (4-6) is obtained as follows, for example. That is, the following formula (4-11)

In the presence of a basic compound such as sodium carbonate in a polar solvent such as xylene, 1 to 3 mol of benzoyl acetate ethyl ester is added to 1 mol of an anthraquinone compound represented by the formula (wherein R ₂₁ represents the same meaning as described above). Reaction is performed at 130 to 180 ° C. for 5 to 15 hours, and the following formula (4-12)

(Wherein R ₂₁ represents the same meaning as described above).

  Next, 1 to 5 mol of metaaminoacetanilide is added to 1 mol of the compound of the formula (4-12) in an aprotic polar organic solvent such as N, N-dimethylformamide and a base such as sodium carbonate and copper acetate. In the presence of a copper catalyst, condensation is carried out by carrying out Ullmann reaction at 110 to 150 ° C. for 2 to 6 hours.

(Wherein R ₂₁ represents the same meaning as described above).

  Subsequently, the compound of formula (4-13) is sulfonated at 8 to 15% fuming sulfuric acid at 50 to 120 ° C. and the acetylamino group is hydrolyzed to obtain a compound of the general formula (4-6)

(Wherein R ₂₁ represents the same meaning as described above).

[Compound represented by formula (5)]

In the general formula (5), R ₃₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₃₁ represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.
M ⁵ represents a hydrogen atom or a counter cation. M ⁵ may be the same or different from each other.
X ₃₁ represents a group represented by the following general formula (5-1).

In General Formula (5-1), R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —COOM ′ (M ′ is Represents a hydrogen atom or a counter cation). However, at least one of R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represents an alkyl group having 1 to 8 carbon atoms or —COOM ′.

In the general formula (5), R ₃₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.

Specific examples of the alkyl group and the substituent when R ₃₁ represents a substituted or unsubstituted alkyl group are the same as R ₂₁ in the general formula (4).

R ₃₁ is preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group from the viewpoint of availability of raw materials.

In General Formula (5), Y ₃₁ represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.

Specific examples and preferred ranges when Y ₃₁ represents a substituted or unsubstituted amino group are the same as those of Y ₂₁ in the general formula (4).
Y ₃₁ is preferably a chlorine atom, a hydroxyl group, or an amino group, more preferably a hydroxyl group or an amino group, and still more preferably a hydroxyl group, from the viewpoint of moisture resistance.

In the general formula (5), X ₃₁ represents a group (substituted anilino group) represented by the following general formula (5-1).

In General Formula (5-1), R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —COOM ′ (M ′ is Represents a hydrogen atom or a counter cation). However, at least one of R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represents an alkyl group having 1 to 8 carbon atoms or —COOM ′.

When R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represent an alkyl group having 1 to 8 carbon atoms, the alkyl group having 1 to 8 carbon atoms is preferably a linear or branched alkyl group, Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-octyl group.
In the case of an alkyl group, considering the hue, at least one of R ₃₂ and R ₃₆ is preferably an alkyl group, and the other is preferably a hydrogen atom. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.

M ′ represents a hydrogen atom or a counter cation. Examples of the counter cation include monovalent counter cations, and alkali metal ions (preferably lithium ions, sodium ions, and potassium ions, and sodium ions are more preferable), ammonium ions, and organic cations are preferable. Examples of the organic cation include a cation obtained by adding a hydrogen ion to an alkylamine or alkanolamine. Examples of the alkylamine include trimethylamine and triethylamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.
M ′ is preferably a hydrogen atom or an alkali metal ion.

The R ₃₂ to R _36, an alkyl group or -COOM 'is preferably 1 to 8 carbon _atoms, among R 32 _{to R 36,} 1 to 3, more preferably 1 to 2 of these groups, The case where the other is a hydrogen atom is preferable.
When two of these are groups other than hydrogen atoms, R ₃₂ and R ₃₆ or R ₃₃ and R ₃₅ are preferably groups other than hydrogen atoms, and when three are groups other than hydrogen atoms. In R, R ₃₂ , R ₃₄ and R ₃₆ are preferably groups other than hydrogen atoms. More preferably, it is a case where 1 to 3 of R _{32 to} R ₃₆ are —COOM ′ and the other is a hydrogen atom. More preferably, at least one of R ₃₂ , R ₃₃ or R ₃₅ is —COOM ′.

Specific examples of X ₃₁ include, for example, 2-methylanilino group, 2,6-dimethylanilino group, 2,5-dimethylanilino group, 2,4,6-trimethylanilino group, 2,6-diethylanilino. Group, 2,5-diethylanilino group, 2,6-di-iso-propylanilino group, 2,5-di-iso-propylanilino group, 2-carboxyanilino group, 3-carboxyanilino group 4-carboxyanilino group, 2,5-dicarboxyanilino group, 3,5-dicarboxyanilino group, 5-carboxy-2-methylanilino group, 5-carboxy-2-ethylanilino group and the like.

X ₃₁ represents 2,6-dimethylanilino group, 2,4,6-trimethylanilino group, 2,6-diethylanilino group, 2,6-di-iso-propylanilino group, 2-carboxyaniline. A lino group or a 3,5-dicarboxyanilino group is preferable, a 2,6-dimethylanilino group, a 2,6-diethylanilino group, a 2,6-di-iso-propylanilino group, a 2-carboxyaniline group. A lino group or a 3,5-dicarboxyanilino group is more preferred, and a 2-carboxyanilino group or a 3,5-dicarboxyanilino group is more preferred.

In the general formula (5), M ⁵ represents a hydrogen atom or a counter cation. M ⁵ may be the same or different from each other.
In the general formula (5), when M ⁵ is a hydrogen atom, it is in the form of a free acid, and when M ⁵ is a counter cation, it is in the form of a salt.
Examples of counter cations that form salts include monovalent counter cations, and alkali metal ions, ammonium ions, organic cations, and the like are preferable.
Examples of the organic cation include a cation obtained by adding a hydrogen ion to an alkylamine or alkanolamine. Examples of the alkylamine include trimethylamine and triethylamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.
From the viewpoint of water solubility, alkali metal ions are preferable, and lithium ions, sodium ions, and potassium ions are more preferable. In particular, sodium ions are preferred from the viewpoint of inexpensive production.
In the general formula (5), M ⁵ may be the same or different. That is, the compound represented by the general formula (5) is in the form of a salt when all the sulfo groups are in the form of a salt and when some of the sulfo groups are in the form of a free acid. This includes the case where the sulfo group in part is a salt. Moreover, the counter cation forming the salt may be one kind or plural kinds.
The group other than the sulfo group that can be in the form of a salt (for example, a carboxyl group) is the same as described above.

  Specific examples of the anthrapyridone compound represented by the general formula (5) are shown in Table 3. In Table 3, (K) means a carboxy group, and 2 (K) means a dicarboxy group. In the following specific examples, the sulfo group may be in a salt state.

A method for synthesizing the compound represented by the general formula (5) will be described.
The anthrapyridone compound of the general formula (5) is produced, for example, by the following method. That is, the following formula (5-2)

(Wherein R ₃₁ represents the same meaning as above) 1 mol of 2,4,6-trichloro-S-triazine (cyanuric chloride) 1 to 1.3 mol in water at pH 2 to 7, Formula (5-3) which is a primary condensate obtained by reacting at 5-35 ° C. for 2-8 hours

By reacting 1 mol of the corresponding anilines with the compound of the formula (wherein R ₃₁ represents the same meaning as described above) at pH 4 to 9, 5 to 90 ° C., 10 minutes to 5 hours, Y ₃₁ is chlorine. Formula (5-4) which is an atom

(Wherein R _{31 to} R ₃₆ represent the same meaning as described above), and a compound is obtained as a secondary condensate. Then, it is hydrolyzed by pH 9-12, 50-100 ° C., 10 minutes-5 hours, or by reacting ammonia and the corresponding amines at pH 8-10, 50-100 ° C., 10 minutes-8 hours. Formula (5-5) in which Y ₃₁ is not a chlorine atom as a condensate

(Wherein R _{31 to} R ₃₆ and Y ₃₁ represent the same meaning as described above).

  The order of condensation is appropriately determined according to the reactivity of various compounds, and is not limited to the above.

  The compound thus obtained exists in the form of the free acid or in the form of its salt. The method for producing the salt is the same as the method for producing the salt in the compound represented by the general formula (4).

The anthrapyridone compound of the formula (5-2) can be obtained in the same manner as in the synthesis example of the anthrapyridone compound of the formula (4-6) in the synthesis method of the general formula (4). Incidentally, _{R 21} in the formula (4-6) _is read as _{R 31, R 31} in the formula (5-2) are as defined above.

(Coloring composition)
The colored composition of the present invention includes at least one selected from the group consisting of a compound represented by the general formula (1), a compound represented by the general formula (4), and a compound represented by the general formula (5). Containing. The compound represented by the general formula (4) or the general formula (5) may be either of them or both of them may be included. A combination of the compound represented by the general formula (1) and at least one selected from the group consisting of the compound represented by the general formula (4) and the compound represented by the general formula (5) Due to the synergistic effect (deactivation due to intermolecular energy transfer of excitation energy, permeability control in a printing medium, etc.), it is possible to achieve both good fastness and good printing density.
The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention uses a lipophilic medium or an aqueous medium as a medium, and includes a compound represented by the general formula (1), a compound represented by the general formula (4), and a general It can be produced by dissolving and / or dispersing at least one selected from the group consisting of compounds represented by formula (5). Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In this invention, content of the compound of this invention contained in a coloring composition is used in order to manufacture the kind of substituent in General formula (1), (4), (5) used, and a coloring composition. The content of the compound represented by the general formula (1) in the colored composition is preferably 1 to 20% by mass with respect to the total mass of the colored composition, although it is determined by the type of the solvent component and the like. It is more preferable that 1-10 mass% is contained, and it is still more preferable that it is 2-6 mass%.

  By making the content of the compound represented by the general formula (1) contained in the coloring composition 1% by mass or more, it is possible to improve the color development of the ink on the recording medium when printed, and it is necessary. Image density can be ensured. Moreover, when the content rate of the compound represented by General formula (1) contained in a coloring composition shall be 20 mass% or less, when it uses for an inkjet recording method, the discharge property of a coloring composition can be made favorable. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  The total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) in the coloring composition is the stability over time of the coloring composition when used in the inkjet recording method. From the viewpoint of dischargeability, the content is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 6% by mass with respect to the total mass of the colored composition.

  In the colored composition, the mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) Is preferably 9/1 to 1/9, more preferably 8/2 to 1/9, and still more preferably 5/5 to 1/9. By setting the mass ratio within the above range, it is preferable from the viewpoint of ozone resistance, light resistance, moisture resistance and print density.

  The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The present invention also relates to an inkjet recording ink containing the coloring composition of the present invention.
The ink for inkjet recording can be prepared by dissolving and / or dispersing the compound (mixture) of the present invention in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
If necessary, other additives can be contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for ink jet recording at the ink ejection port of the nozzle used in the ink jet recording method.

  As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration accelerator is preferably used for the purpose of allowing the ink for ink jet recording to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjusting agent is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the ink for ink jet recording of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the compound of the present invention is dispersed in an aqueous medium, as described in JP-A Nos. 11-286637, 2000-78491, 2000-80259, 2000-62370, and the like, Colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or as described in Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857. It is preferable that the compound of the present invention dissolved in a high boiling point organic solvent is dispersed in an aqueous medium. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to. Alternatively, the compound of the present invention may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  In 100 parts by mass of the inkjet recording ink of the present invention, the compound of the present invention is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less. In addition, in the ink for inkjet recording of the present invention, other dyes may be used in combination with the compound of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above range.

  The ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  The ink for inkjet recording of the present invention can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Any yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.

  The ink composition of the present invention can be used in recording methods such as printing, copying, marking, writing, drawing, stamping, and the like, and is particularly suitable for use in an inkjet recording method.

[Inkjet recording method]
The present invention also relates to an inkjet recording method for forming an image using the colored composition or the inkjet recording ink of the present invention.
In the ink jet recording method of the present invention, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. To do.

  When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-297365, etc. The method described in the specification can be preferably used.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m 2.
The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support.
It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,2,387,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-resistant agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

Hereinafter, although the synthesis method of the compound (mixture) of this invention is demonstrated in detail to an Example, this invention is not limited to these Examples at all. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.
In addition, Example 12 shall be read as Reference Example 12.

(Synthesis example)
Synthesis of Compound (1A) In a 150 mL three-necked flask, 60 g of chlorosulfonic acid (manufactured by Acros) and 6.2 g of phosphorus oxychloride (manufactured by Fischer) are added and stirred at room temperature. 9.54 g (manufactured by CHUGAI AMINOL FAST PINKR) was carefully added, then heated to 70 ° C. and reacted for 1 hour. The reaction solution was cooled to room temperature, quenched with 300 g of ice water, and the precipitated crystals were separated by filtration and washed with cold saturated brine. The obtained crystals were dispersed in 150 mL of water, and the dropwise addition was continued using 2 mol / L sodium hydroxide until the pH became constant at 9.0. When there is no change in pH, the pH is adjusted to 8.5 using dilute hydrochloric acid of 0.2 mol / L, desalting is performed using a dialysis tube, and dust removal is performed using a GF / F filter (Whatman). And dried with a blow dryer at 60 ° C. to obtain 6 g of green glossy crystals. The absorption maximum wavelength in the diluted aqueous solution was 529 nm. In the LC-MS spectrum measured under the following conditions, three components having a retention time of 7.12 minutes, 8.32 minutes, and 10.08 minutes were observed, and the molecular weight thereof was 894 (Posi: 895 [M + 1]). ⁺ , Nega: 446.2 [M-2H] ²⁻ ).

(LC-MS conditions)
Column Genesis C18 (100 x 4.6 mm)
Temperature 40 ℃
Eluent A 10 mM ammonium acetate aqueous solution eluent B 10 mM ammonium acetate acetonitrile / water (90/10) solution gradient 0 min (B concentration 5%), 2 min (B concentration 5%), 25 min (B concentration 50%), 30 minutes (B concentration 95%), 31 minutes (B concentration 5%), 40 minutes (B concentration 5%)
Flow rate 1.0 mL / min Detection wavelength 200-700 nm
MS (range) 200-1200
Injection volume 10μL

FIG. 1 shows a ¹ H NMR spectrum of compound (1A) in deuterated dimethyl sulfoxide.

  Other exemplary compounds can also be synthesized according to the above method.

The following compounds (4A), (4B), and (4C) were synthesized with reference to JP-A No. 2003-192930.
The following compounds (5A), (5B), and (5C) were synthesized with reference to WO 04/104108.

[Example 1]
Deionized water was added to the following components to make 100 g, and the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare a magenta ink liquid.

Compound of general formula (1) (the following compound (1A)) 0.5 g
Compound of general formula (4) (the following compound (4A)) 3.0 g
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Olfin E1010 (Nissin Chemical Industry Co., Ltd.) 0.9g

[Examples 2 to 16 and Comparative Examples 1 to 4]
Ink liquids of Examples 2 to 16 and Comparative Examples 1 to 4 were prepared in the same manner as the preparation of the ink liquid of Example 1, except that the dye and the dye addition amount were changed as shown in Table 4 below. As a comparative dye, C.I. I. Acid Red 289 (AR289) was used.

(Image recording and evaluation)
The following evaluation was performed on the inks for ink jet recording of the above Examples and Comparative Examples. The results are shown in Table 4.
In Table 4, the ozone resistance, light resistance, and moisture resistance of each ink-jet recording ink were measured with a photo glossy paper (EPSON PM photo paper < Evaluation is performed after an image is recorded in glossy> (KA420PSK, EPSON)). The print density was evaluated after each ink-jet recording ink was recorded on plain paper (Canon plain paper (GF500, Canon)) with an inkjet printer (manufactured by EPSON Corporation; PM-700C). .

<Ozone resistance>
While passing dry air through a double glass tube of a Siemens type ozonizer, an AC voltage of 5 kV was applied, and using this, the image was placed in a box set at an ozone gas concentration of 5 ± 0.1 ppm, room temperature, in a dark place. The formed photo glossy paper was allowed to stand for 7 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Light resistance>
After measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165), and the image density Cf was measured again. The dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated and evaluated from the difference in image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer (X-Rite 310TR).
The dye residual ratio was measured at three points with reflection densities of 1, 1.5 and 2.0. At any concentration, the evaluation was made in three stages: A when the dye residual ratio was 80% or more, B as 1 or 1 or 2 points less than 80%, and C as less than 80% at all concentrations.

<Moisture resistance>
During ink-jet recording, a check pattern (a pattern in which squares having a 1.5 mm square with a density of 100% and 0% were alternately combined) was created to obtain a magenta-white check pattern print with high contrast. . After printing, the printed matter with the check pattern dried for 24 hours is allowed to stand for 3 days under the condition of 80 ° C. and 70% RH, and the degree of bleeding from the colored portion to the white portion is visually evaluated. Evaluation was made in three stages, where B was slightly blurred and C was clearly blurred.

<Print density>
The reflection density at a printing density of 100% is measured using a reflection densitometer (X-Rite 310TR), and the printing density is 2.2 or more, A, 2.0 to less than 2.2, and B, The case of less than 2.0 was defined as C and evaluated in three stages.

  As is clear from the results in Table 4, the inks of the examples using the coloring composition of the present invention have extremely high ozone resistance, light resistance, moisture resistance, and print density compared to the inks of the comparative examples. It turns out that it has performance.

Claims (15)

A compound represented by the following general formula (1):
At least one selected from the group consisting of a compound represented by the following general formula (4) and a compound represented by the following general formula (5);
A coloring composition comprising:

In general formula (1), D represents the residue remove | excluding n hydrogen atoms from the compound represented by the following general formula (2), and n represents the number of 4-6 . M represents a hydrogen atom or a counter cation.
M may be the same or different.

In general formula (2), R ¹⁰¹ , R ¹⁰² , and R ¹⁰³ each independently represents a monovalent substituent, R ¹⁰⁴ and R ¹⁰⁵ each independently represent a hydrogen atom or a monovalent substituent, and n 101 and n102 represents the number of 0-5 each independently, and n103 represents the number of 0-4. n101, if n102 and n103 represents the number of 2 or more, respectively, a plurality of ^{R 101, R 102,} and ^{R 103} may be different even in the same.

In general formula (4), R ₂₁ and R ₂₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₂₁ and Y ₂₂ each independently represent a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, an alkoxy group, or a substituted or unsubstituted phenoxy group.
X represents a divalent linking group.
M ⁴ represents a hydrogen atom or a counter cation. M ⁴ may be the same or different from each other.

In the general formula (5), R ₃₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Y ₃₁ represents a chlorine atom, a hydroxyl group, a substituted or unsubstituted amino group, or a morpholino group.
M ⁵ represents a hydrogen atom or a counter cation. M ⁵ may be the same or different from each other.
X ₃₁ represents a group represented by the following general formula (5-1).

In General Formula (5-1), R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or —COOM ′ (M ′ is Represents a hydrogen atom or a counter cation). However, at least one of R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , and R ₃₆ represents an alkyl group having 1 to 8 carbon atoms or —COOM ′.   The coloring composition according to claim 1, wherein n in the general formula (1) is 4. The colored composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

In General Formula (3), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent a monovalent substituent, n201 and n202 each independently represent a number from 0 to 4, and n203 is a number from 0 to 4 Represents. n201, n202, and if n203 represents the number of 2 or more, respectively, a plurality of ^{R 201, R 202,} and ^{R 203} may be different even in the same. M represents a hydrogen atom or a counter cation. M may be the same or different. The coloring composition according to any one of claims 1 to 3, wherein each of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ independently represents an alkyl group or an acylamino group. The colored composition according to claim 1, wherein R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an alkyl group having 1 to 6 carbon atoms. object.   The coloring composition according to any one of claims 1 to 5, wherein each of n101, n102, n201, and n202 independently represents a number of 2 to 4.   The colored composition according to claim 1, wherein n103 and n203 represent 0.   The coloring composition as described in any one of Claims 1-7 whose said M is a lithium ion, a sodium ion, or a potassium ion. The colored composition according to claim 1, wherein R ₂₁ , R ₂₂ , and R ₃₁ are each independently a hydrogen atom or an unsubstituted alkyl group. The colored composition according to claim 1, wherein Y ₂₁ , Y ₂₂ , and Y ₃₁ are each independently a chlorine atom, a hydroxyl group, or an unsubstituted amino group.   The content rate of the compound represented by General formula (1) is 1-20 mass%, The coloring composition as described in any one of Claims 1-10.   The coloring composition according to any one of claims 1 to 11, wherein the total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) is 1 to 20% by mass. object.   The mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) and the compound represented by the general formula (5) is 9/1 to It is 1/9, The coloring composition as described in any one of Claims 1-12.   Ink for inkjet recording containing the coloring composition as described in any one of Claims 1-13.   The inkjet recording method of forming an image using the coloring composition as described in any one of Claims 1-13, or the ink for inkjet recording of Claim 14.

Images