JP2013049777A - New compound having triazine side chain, coloring composition, inkjet recording ink, inkjet recording method, color filter and color toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound of specific structure having a specific triazine unit on the side chain and derived from an azo dye, which gives printed matter excellent in moisture resistance and further improved of performances concerning image robustness such as ozone resistance and light resistance, than before.SOLUTION: There is disclosed a coloring composition, for example, including a compound expressed by chemical formula, wherein 0≤l≤3; 0≤m≤3; 1≤n≤4; and l+m+n=4.

Description

  The present invention relates to a novel compound having a triazine side chain, a coloring composition containing the compound, an ink for ink jet recording, an ink jet recording method, a color filter, and a color toner.

  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 danger on fire fighting. These inks have appropriate physical properties such as viscosity and surface tension, nozzle clogging, excellent storage stability, and high density recording images, as well as light resistance, water resistance, and moisture resistance. Properties such as excellent properties are required.

  Many of these performances are satisfied by using a water-based ink whose main solvent is water or a mixture of water and a water-soluble organic solvent, but color tone, vividness, light resistance, water resistance, moisture resistance, etc. Depends greatly on the colorant, and various dyes have been studied.

  In particular, in a color recording method using a plurality of colors of ink, uniform characteristics are required for all the inks constituting the ink. In particular, the magenta dye has problems that fading and color tone change due to ozone and light (sunlight, fluorescent lamp, etc.) are significantly larger than other dyes (cyan dye, yellow dye). Therefore, the ozone resistance and light resistance of magenta ink are inferior to those of other inks, resulting in a change in color tone of the entire printed image due to fading of magenta ink, resulting in a loss of quality.

  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, although they are highly water-soluble, nozzle clogging is unlikely to occur, but the performance of ozone resistance and moisture resistance is very high. It was low.

Therefore, Patent Document 1 discloses a magenta inkjet recording liquid containing an azo dye in which two types of heterocycles are linked by an azo group, and is excellent in light resistance and ozone resistance of a color image, and in water resistance. It is also described that it is excellent.
Further, Patent Document 2 discloses a phthalocyanine dye ink having excellent light resistance, ozone resistance and moisture resistance by having a triazine side chain having a specific structure.

Patent No. 4095807 Japanese Patent No. 4420267

However, the coloring matter described in Patent Document 1 requires further improvement in performance (for example, ozone resistance and moisture resistance) when used as an inkjet ink, and there is room for investigation.
An object of the present invention is to provide an excellent dye having further improved image fastness such as ozone resistance and moisture resistance.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that a novel compound having a specific structure derived from an azo dye, in which a triazine unit having a specific linking group is introduced into the side chain, has ozone resistance and light resistance. The present inventors have found that the performance relating to image fastness such as the above is further improved and the moisture resistance is excellent, and the present invention has been completed.

  That is, the present invention is as follows.

一般式（１）中、Ｒ^０〜Ｒ^３はそれぞれ独立に、水素原子又は置換基を表す。また、Ｒ^０とＲ^１は互いに結合して環を形成してもよい。
Ｌは、単結合又は２価の連結基を表す。
Ｄは、一般式（２）で表される化合物から水素原子をｎ個取り除いた残基を表す。
ｎは、１以上の整数を表す。但し、ｎが２以上の整数を表す場合、複数のＲ^０〜Ｒ^３、及びＬは、それぞれ同一でも異なっていてもよい。
一般式（２）中、Ｒ^１１は、水素原子、アルキル基、シクロアルキル基、アラルキル基、アリール基、ヘテロ環基又はアシル基を表す。各置換基は、さらに置換されていてもよい。
Ｒ^１２は、水素原子、ハロゲン原子、又はシアノ基を表す。
Ｒ^１３は、水素原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アリール基、ヘテロ環基、カルボキシル基、又はスルホ基を表す。各置換基はさらに置換されていてもよい。
Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は、各々独立して、水素原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アリール基、ヘテロ環基、スルホニル基、アシル基、カルボキシル基、スルホ基、又はカルバモイル基を表す。各置換基はさらに置換されていてもよい。ただし、Ｒ_１４とＲ^１５が共に水素原子であることはなく、Ｒ^１６とＲ^１７が共に水素原子であることはない。
Ａ^１及びＡ²は、いずれもが置換されていてもよい炭素原子であるか、あるいはこれらの一方が置換されていてもよい炭素原子であり、他方が窒素原子である。
〔２〕
前記一般式（２）中、Ｒ^１３は、水素原子、置換若しくは無置換のアリール基又は置換若しくは無置換のヘテロ環基である、〔１〕に記載の着色組成物。
〔３〕
前記一般式（２）中、Ｒ^１６が水素原子であって、Ｒ^１４、Ｒ^１５、及びＲ^１７が置換若しくは無置換のアリール基又は置換若しくは無置換のヘテロ環基である、〔１〕又は〔２〕に記載の着色組成物。
〔４〕
一般式（１）中、Ｄは一般式（２）で表される化合物の、Ｒ^１４〜Ｒ^１７から水素原子をｎ個取り除いた残基を表す、〔１〕〜〔３〕のいずれか１項に記載の着色組成物。
〔５〕
〔１〕〜〔４〕のいずれか１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。
〔６〕
〔１〕〜〔４〕のいずれか１項に記載の着色組成物又は〔５〕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。
〔７〕
〔１〕〜〔４〕のいずれか１項に記載の一般式（１）で表される化合物を含有するカラーフィルタ。
〔８〕
〔１〕〜〔４〕のいずれか１項に記載の一般式（１）で表される化合物を含有するカラートナー。
〔９〕
一般式（１）で表される化合物。

一般式（１）中、Ｒ^０〜Ｒ^３はそれぞれ独立に、水素原子又は置換基を表す。また、Ｒ^０とＲ^１は互いに結合して環を形成してもよい。
Ｌは、単結合又は２価の連結基を表す。
Ｄは、一般式（２）で表される化合物から水素原子をｎ個取り除いた残基を表す。
ｎは、１以上の整数を表す。但し、ｎが２以上の整数を表す場合、複数のＲ^０〜Ｒ^３、及びＬは、それぞれ同一でも異なっていてもよい。
一般式（２）中、Ｒ^１１は、水素原子、アルキル基、シクロアルキル基、アラルキル基、アリール基、ヘテロ環基又はアシル基を表す。各置換基は、さらに置換されていてもよい。
Ｒ^１２は、水素原子、ハロゲン原子、又はシアノ基を表す。
Ｒ^１３は、水素原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アリール基、ヘテロ環基、カルボキシル基、又はスルホ基を表す。各置換基はさらに置換されていてもよい。
Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７は、各々独立して、水素原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アリール基、ヘテロ環基、スルホニル基、アシル基、カルボキシル基、スルホ基、又はカルバモイル基を表す。各置換基はさらに置換されていてもよい。ただし、Ｒ^１４とＲ^１５が共に水素原子であることはなく、Ｒ^１６とＲ^１７が共に水素原子であることはない。
Ａ^１及びＡ²は、いずれもが置換されていてもよい炭素原子であるか、あるいはこれらの一方が置換されていてもよい炭素原子であり、他方が窒素原子である。 [1]
The coloring composition containing the compound represented by General formula (1).

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. R ⁰ and R ¹ may be bonded to each other to form a ring.
L represents a single bond or a divalent linking group.
D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2).
n represents an integer of 1 or more. However, when n represents an integer of 2 or more, plural R ⁰ to R ^3, and L may each be the same or different.
In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ₁₄ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.
[2]
In said general formula (2), R < ¹³ > is a coloring composition as described in [1] which is a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
[3]
In the general formula (2), R ¹⁶ is a hydrogen atom, and R ¹⁴ , R ¹⁵ , and R ¹⁷ are a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, [1] or The coloring composition as described in [2].
[4]
In General Formula (1), D represents any one of [1] to [3], which represents a residue obtained by removing n hydrogen atoms from R ^{14 to} R ^{17 in the} compound represented by General Formula (2). The coloring composition according to item.
[5]
Ink for inkjet recording containing the coloring composition of any one of [1]-[4].
[6]
An inkjet recording method for forming an image using the colored composition according to any one of [1] to [4] or the inkjet recording ink according to [5].
[7]
The color filter containing the compound represented by General formula (1) of any one of [1]-[4].
[8]
A color toner containing the compound represented by the general formula (1) according to any one of [1] to [4].
[9]
The compound represented by General formula (1).

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. R ⁰ and R ¹ may be bonded to each other to form a ring.
L represents a single bond or a divalent linking group.
D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2).
n represents an integer of 1 or more. However, when n represents an integer of 2 or more, plural R ⁰ to R ^3, and L may each be the same or different.
In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.

According to the present invention, it is derived from an azo dye having a specific triazine unit in the side chain, which has further improved performance related to image fastness such as ozone resistance and light resistance, and has excellent moisture resistance. A novel compound having a specific structure, a coloring composition containing the compound, an ink for ink jet recording, and an ink jet recording method are provided.
Furthermore, a color filter and a color toner containing the novel compound are provided.

FIG. 1 is a diagram showing a transmission spectrum of the color filter of the present invention.

Hereinafter, the present invention will be described in detail.
First, in the present invention, the substituent group A and the ionic hydrophilic group are defined.
(Substituent group A)
For example, 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 , Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group , Mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarboni Examples include groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, and ionic hydrophilic groups. . These substituents may be further substituted, and examples of the further substituent include groups selected from the substituent group A described above.

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

  Examples of the alkyl group include linear, branched, 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. Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl. Group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like, and the cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms such as cyclohexyl group, A cyclopentyl group, 4-n-dodecylcyclohexyl group and the like. The bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a bicycloalkane having 5 to 30 carbon atoms. Monovalent groups from which one hydrogen atom has been removed, for example, bicyclo [1,2,2] heptan-2-yl group, bicycl [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. Specifically, the alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group, and the like. Is preferably 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 2-cyclopentene-1 -Yl group, 2-cyclohexen-1-yl group and the like, and 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 monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond, 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, an ethylsulfinyl group, phenyl. Examples thereof include a sulfinyl group and a p-methylphenylsulfinyl group.

  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, an ethylsulfonyl group, or a phenyl group. A sulfonyl group, p-methylphenylsulfonyl group, etc. are mentioned.

  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.

(Ionic hydrophilic group)
A sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, a quaternary ammonium group and the like can be mentioned. 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, lithium salt or mixed salt containing lithium salt as a main component Are more preferred, and lithium salts are most preferred.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the ink, but is expressed as “contains a salt” for convenience.

Below, the compound represented by General formula (1) of this invention is demonstrated in detail.
[Compound represented by the general formula (1)]
The compound represented by the general formula (1) of the present invention includes a compound, a salt thereof, and a hydrate thereof.
The compound of the present invention is characterized in that an amino group substituted with a triazinyl group is introduced via a specific linking group. Although the mechanism of action is unknown, it is excellent in image fastness such as ozone resistance and light resistance as compared with a compound not having these characteristics. In addition, the intermolecular hydrogen bond has the same effect as when the molecular weight is increased, it can suppress the movement of molecules in the printed material when it is formed, and exhibits excellent moisture resistance. To do.

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. R ⁰ and R ¹ may be bonded to each other to form a ring.
L represents a single bond or a divalent linking group.
D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2).
n represents an integer of 1 or more. However, when n represents an integer of 2 or more, plural R ⁰ to R ^3, and L may each be the same or different.

In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the above-described substituent group A.

R ⁰ and R ¹ are preferably a hydrogen atom or the above-mentioned substituent group A. A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkenyl group is preferred, a hydrogen atom or a substituted or unsubstituted alkyl group is more preferred, and a hydrogen atom is still more preferred.

R ² and R ³ are preferably a hydrogen atom or the above substituent group A, a hydrogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted group Alternatively, an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a substituted or unsubstituted heterocyclic thio group are preferable, and a substituted or unsubstituted amino group is more preferable. The substituents represented by R ² and R ³ may be bonded to each other to form a ring.
Examples of the substituent when the substituent represented by R ² and R ³ further has a substituent include the substituent group A, and an alkyl group, an aryl group, or a heterocyclic group is preferable. These may be further substituted with the substituent group A, and more preferably substituted with an ionic hydrophilic group.

In general formula (1), L represents a single bond or a divalent linking group. Examples of the divalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), and methylene. Examples include a group (—CH ₂ —), an arylene group, a cycloalkylene group, a heterocyclic group, and a group formed by combining these. Preferably, L is an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted cycloalkylene group, or a heterocyclic group, more preferably 2 to 6 carbon atoms. An alkylene group; When L has a substituent, examples of the substituent include the substituent group A, and an alkyl group is preferable. The substituent of L and R ¹ may be bonded to each other to form a ring.

  Specific examples of the divalent linking group represented by L include the following examples.

D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2), and n hydrogen atoms are removed from R ^{14 to} R ¹⁷ of the compound represented by the general formula (2). Preferably, it represents a residue.

  n represents an integer of 1 or more. n is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

  Specific examples of the specific linking group shown in parentheses of the general formula (1) and a substituent (triazine unit) containing an amino group substituted with a triazinyl group are shown below. The present invention includes these specific examples. It is not limited.

In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.

R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group, and each substituent may be further substituted.
The alkyl group includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a t-butyl group. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
The cycloalkyl group includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group includes an aralkyl group having a substituent and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group.
The aryl group includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl.

The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group and 2-furyl group.
The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms excluding the carbon atoms of the substituent. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, It represents a sulfo group or a carbamoyl group, and each substituent may be further substituted.
The alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group and acyl group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are as defined above for R ¹¹ .
The alkenyl group includes an alkenyl group having a substituent and an unsubstituted alkenyl group. As the alkenyl group, an alkenyl group having 5 to 12 carbon atoms excluding the carbon atoms of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group and an allyl group.
The sulfonyl group includes an alkylsulfonyl group such as a methanesulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group.

R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group, and each of these substituents may be further substituted. Examples of these substituents are the same as those for R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ above.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of these is a carbon atom that may be substituted, and the other is a nitrogen atom. Examples of the substituent of the carbon atom which may have a substituent include the same as those described above for R ¹⁴ , R ¹⁵ , R ¹⁶ and R ^17, and preferred ones are also the same.

Regarding the general formula (1), examples of preferred substituents represented by R ^{11 to} R ¹⁷ , A ¹ and A ² are shown below.
R ¹¹ is preferably an alkyl group or an aryl group. Furthermore, among the alkyl groups, an isopropyl group or a t-butyl group is more preferable, and a t-butyl group is more preferable. The aryl group is preferably a phenyl group and a phenyl group having a further substituent at any of the 2-position, 4-position or 6-position when viewed from the pyrazole mother nucleus side.
R ¹² is most preferably a cyano group.

R ¹³ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. R ₁₃ is more preferably a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and when these further have a substituent, the substituent is an electron withdrawing group. Is more preferable.
When R ¹³ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, it is preferable in terms of ozone resistance.
Here, Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it can be found in the above-mentioned book and is limited only to a substituent having a known value in the literature. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule.

The electron-withdrawing group in R ¹³ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.
Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, heterocyclic group, halogen atom, azo group, selenocyanate group, and other electron withdrawing groups with a σp value of 0.20 or more An aryl group selected Preferably, they are a cyano group, a nitro group, and a halogen atom. The heterocyclic group may or may not be substituted with an electron withdrawing group.

As described above, both A ¹ and A ² are carbon atoms that may be substituted, or one of these is a carbon atom that may be substituted, and the other is a nitrogen atom. . A case in which both A ¹ and A ² are carbon atoms is preferable in that a more excellent performance can be exhibited.
Additional substituents on the carbon atoms represented by A ¹ and A ^2, an alkyl group having 1 to 3 carbon atoms, a carboxyl group, a carbamoyl group, a cyano group, more preferably an alkyl group having 1 to 3 carbon atoms.

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an optionally substituted alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, acyl group, heterocyclic group. It preferably represents a carboxyl group or a sulfo group.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an aryl group, a sulfonyl group, an acyl group, or a heterocyclic group. It is preferably a hydrogen atom, an optionally substituted sulfonyl group, an acyl group, an aryl group or a heterocyclic group, particularly preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. preferable.
R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
R ¹⁶ is preferably a hydrogen atom from the viewpoint of light resistance, more preferably R ¹⁶ is a hydrogen atom, R ¹⁴ , R ¹⁵ and R ¹⁷ are not hydrogen atoms, and R ¹⁶ is a hydrogen atom. It is more preferable that R ¹⁴ , R ¹⁵ , and R ¹⁷ are a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

The substituent in the case where R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ further have a substituent can include the substituent group A, and includes an alkyl group having 1 to 8 carbon atoms, a sulfo group, a chlorine atom, a substituent or An unsubstituted sulfamoyl group is preferred, and a sulfo group or a substituted or unsubstituted sulfamoyl group is preferred. Examples of the substituent of the substituted sulfamoyl group include the substituent group A, and a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms substituted with a hydroxyl group is preferable. More preferred.

When the compound represented by the general formula (1) of the present invention is used as a water-soluble dye, R ⁰ , R ¹ , R ² , R ³ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ are: It is preferably substituted with at least two or more sulfo groups or carboxyl groups, and more preferably substituted with three or more sulfo groups or carboxyl groups.

  Hereinafter, although the specific example of the compound of this invention represented by General formula (1) is given, this invention is not necessarily limited to these specific examples. In addition, * in a specific example represents the substitution position of a substituent.

〔Production method〕
The manufacturing method of the compound represented by General formula (1) of this invention is demonstrated. The compound represented by the general formula (1) is obtained by chlorosulfonylating the compound represented by the following general formula (2) and converting it to the following general formula (3), and then preparing the following general formula (4) separately prepared. It can be easily obtained by reacting. Details will be described below.

In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.

(In General Formula (3), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ and A ² are R ¹¹ , R ¹² , R ¹³ in General Formula (2). , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , A ¹ and A ² , and x represents an integer of 1 to 8.)

(In the general formula ^{(4), R 0, R} 1, R 2, R 3 and L are the same as ^{R 0, R 1, R 2} , R 3 and L in the general formula (1), H is hydrogen Represents an atom.)

  The compound represented by the general formula (2) can be synthesized by a conventionally known method. For example, it can be produced by the method described on page 37 of US7648943B2.

  Next, the compound represented by the general formula (3) will be described.

The compound represented by the general formula (3) can be obtained by chlorosulfonating the compound represented by the general formula (2) in chlorosulfonic acid. Alternatively, the compound represented by the general formula (2) is chlorinated after sulfonation using a sulfonating agent such as concentrated sulfuric acid, 10% to 60% fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, amidosulfuric acid, etc. It can also be obtained by converting a sulfo group to a chlorosulfo group with an agent.
The chlorosulfonation of the compound represented by the general formula (2) is usually preferably performed using 3 to 20 times, preferably 5 to 10 times the amount of chlorosulfonic acid of the compound. The reaction temperature is usually 80 to 150 ° C, preferably 100 to 120 ° C. The reaction time varies depending on the reaction conditions such as the reaction temperature, but is usually 1 to 10 hours. In this case, usually, not all of them are chlorosulfonated, and the sulfo group of the reaction intermediate remains. If necessary, it is preferable to carry out the reaction by further adding a chlorinating agent after the reaction so that all the substituents are chlorosulfonated. Examples of the chlorinating agent include, but are not limited to, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. The addition amount of the chlorinating agent is about 0.5 to 10 equivalents, preferably about 0.5 to 5 equivalents, with respect to the chlorosulfo group of the target compound.

  Next, the compound represented by the general formula (4) will be described. The organic amine compound represented by the general formula (4) can be synthesized by a conventionally known method. For example, it can be produced by a method described in paragraph No. [0106] of WO2009 / 084195. Details are illustrated in the examples.

  The compound represented by the general formula (1) is usually pH 8 in an aqueous solvent together with the compound represented by the general formula (3), the compound represented by the general formula (4), and if necessary, an amine compound. Can be synthesized by reacting for 1 to 72 hours at 0 to 80 ° C. Examples of the amine compound include ammonia, a substituted or unsubstituted mono- or dialkylamine having 1 to 20 carbon atoms (for example, 2-aminoethanol, 3-aminopropane-1,2 diol, etc.).

  In addition, although the usage-amount of the compound represented by the said General formula (4) is usually 1 time mole or more of the theoretical value according to the value of n with respect to the compound represented by the said General formula (3), Since it changes with the reactivity and reaction conditions of the compound represented by Formula (4), it is not limited to these.

Since this reaction condition is not anhydrous, a part of the chlorosulfonyl compound represented by the general formula (3) is hydrolyzed by water mixed in the reaction system and converted into a sulfo group. It is theoretically considered to contain a sulfo group. In this specification, from the analysis by the integration ratio of ¹ H NMR, the introduction amount of the general formula (4) and the amine compound is calculated, and the rest is expressed as a value calculated as a hydrolyzate.

  The compound represented by the general formula (1) of the present invention synthesized by the above method is obtained in the form of a free acid or a salt thereof. In order to obtain the free acid form, for example, an acid precipitation method is used, and in order to obtain the salt form, for example, a salting out method may be used. When a desired salt cannot be obtained by salting out, a normal salt exchange method such as using an ion exchange resin may be used.

(Coloring composition)
The coloring composition of the present invention contains at least one compound represented by the above general formula (1) of the present invention. 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 can be prepared by dissolving and / or dispersing the compound of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In the present invention, the content of the compound of the present invention contained in the colored composition is determined by the type of substituent in the general formula (1) used, the type of solvent component used for producing the colored composition, and the like. However, the content of the compound represented by the general formula (1) or the salt thereof in the colored composition is preferably 1 to 15% by mass with respect to the total mass of the colored composition, and 1 to 12% by mass. % Is more preferable.

  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 developability of the ink on the recording medium when printed, and it is necessary. Image density can be ensured. Moreover, when the total amount of the compounds represented by the general formula (1) contained in the coloring composition is 10% by mass or less, the discharging property of the coloring composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  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 are 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-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.

  As the anti-drying agent, 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 enhancer is preferably used for the purpose of allowing the ink for inkjet 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 adjuster is preferably added to summer for pH 6 to 10 and more preferably pH 7 to 10 for summer. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the inkjet ink 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 inkjet ink of the present invention, other pigments 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); Azomethine dyes having open-chain active methylene compounds, etc .; 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 magenta dye that can be used in combination with the magenta dye of the present invention 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 thereof 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 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 ink jet 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, 4,283,853, 4,282,305, 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-proofing 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.

[Color filter]
The present invention also relates to a color filter containing the compound represented by the general formula (1).
As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175653. Thus, there is a method of forming a pattern with a photoresist to which a dye is added. Any of these methods may be used as a method used when the compound of the present invention is introduced into a color filter. Preferred methods are described in JP-A-4-175753 and JP-A-6-35182. The positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating on a substrate, exposing through a mask and developing the exposed portion. Then, a positive resist pattern is formed, the positive resist pattern is exposed on the entire surface, and then the exposed positive resist pattern is cured, and a color filter forming method can be mentioned. In addition, a black matrix can be formed according to a conventional method to obtain an RGB primary color system or Y, M, C complementary color system color filter. In the case of a color filter, the amount of the compound of the present invention is not limited, but is preferably 0.1 to 50% by mass.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

[Color toner]
The present invention also relates to a color toner containing the compound represented by the general formula (1).
The content of the compound of the present invention in 100 parts by weight of the color toner is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 to 20 parts by weight, and 2 to 10 parts by weight. Is most preferred. As the binder resin for a color toner into which the compound of the present invention is introduced, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle diameter of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle diameter of this carrier is preferably 30 to 150 μm in terms of volume average particle diameter.

  The image forming method to which the toner is applied is not particularly limited. For example, a method of forming a color image by repeatedly forming a color image on a photoconductor to form an image, or an image formed on a photoconductor For example, a method of sequentially transferring to an intermediate transfer member or the like and forming a color image on the intermediate transfer member or the like and then transferring it to an image forming member such as paper to form a color image, or the like.

(Synthesis example)
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.

Synthesis Example 1: Synthesis of Exemplary Compound 1 Exemplary Compound 1 can be synthesized by the following synthetic route. Details will be described below.

Synthesis of Compound (b) 6 g of Compound (a) was dispersed in 21 g of sulfolane manufactured by Tokyo Chemical Industry, and 5.1 g of sodium sulfan (sulfur trioxide) was added dropwise at an internal temperature of 15 ° C. After completion of dropping, the reaction was allowed to proceed for 2 hours at an internal temperature of 70 ° C. After completion of the reaction, the reaction solution was cooled to 20 ° C., and 6 mL of water was added dropwise. The internal temperature was cooled to 5 ° C., 10 mL of a 25 wt% aqueous sodium hydroxide solution was added dropwise, and 2.4 mL of a sodium methoxide 28 wt% methanol solution was added dropwise. Further, 12 mL of methanol was added dropwise, and the precipitated inorganic salt was filtered and washed with 6 mL of methanol. To this filtrate, 6 g of potassium acetate and 16.8 mL of methanol were added, and 67.5 mL of ethanol was further added to crystallize the dye, followed by suction filtration and washing with ethanol to obtain crude crystal compound (b). Obtained. The crude crystals containing the inorganic salt were desalted and purified by Pharmacia Sephadex LH-20 gel chromatography (eluent, water / methanol = 1: 1 (v / v)), and Li-type ion exchange resin (organo) Amberlite IR-120B-H was neutralized with lithium hydroxide and washed) to give compound (b). Yield 6g, 66% yield. λmax (DMSO) = 567.1 nm, ε = 46900.

Synthesis of Compound (c) 65 g of thionyl chloride was added to a 200 mL flask and stirred at room temperature. After carefully adding 6.0 g of compound (b) slowly thereto, 3 mL of N, N-dimethylformamide was added. The internal temperature was raised to 55 to 60 degrees and reacted for 90 minutes. The reaction solution was added to a solution obtained by dissolving 20 g of sodium chloride in 400 g of ice water, and the precipitated crystals were collected by filtration and washed thoroughly with saturated saline to obtain about 18 g of a wet cake of compound (c).

Synthesis of Compound (d) In a 1000 mL flask, 27.6 g of cyanuric chloride, 100 g of ice water, and 5 drops of calsolene oil were mixed and stirred. Separately, 42.1 g of monosodium aniline-2,5-disulfonate was dispersed in 150 g of water, adjusted to pH 6 using a 2N aqueous sodium hydroxide solution, and slowly dissolved while keeping the internal temperature at 5 ° C. or less. And added. The reaction solution was allowed to react at room temperature for 2 hours while maintaining the pH at 4.5 using an aqueous 2N sodium hydroxide solution. Insoluble matters were removed with a Whatman GF / F filter, and then 16.8 g of dimethylamine was added, followed by stirring overnight at room temperature. The reaction solution was heated to an internal temperature of 40 degrees, 90 g of dimethylamine was added thereto, and the mixture was reacted at 60 degrees for 30 minutes. Sodium chloride corresponding to 10% of the total mass was added, and the pH was adjusted to 1 using concentrated hydrochloric acid. The internal temperature is cooled to room temperature, the precipitated crystals are filtered, washed thoroughly with saturated saline and then with acetone, and then dried overnight in a 60-degree blast dryer to obtain white crystals of compound (d). It was. Based on the results of elemental analysis, this compound was found to have a purity of 82% (the remainder was estimated to be sodium chloride and water).

Synthesis of Exemplary Compound (1) In a 500 mL flask, 2.56 g of compound (d) was dispersed in 100 mL of water, adjusted to pH 8.5 with 2N sodium hydroxide, and dissolved. To this, 2.8 g of 3-amino-1,2-propanediol (e) was added, and then the entire amount of the wet cake obtained by the synthesis of the compound (c) was added. The pH was adjusted to 9.0 using sodium hydroxide, and then the mixture was stirred overnight while the internal temperature was raised to 50 ° C. and the pH was maintained at 9.0. After the reaction solution is almost dissolved, the internal temperature is cooled to 30 ° C., insoluble materials are removed with a Whatman qualitative filter paper, and the resulting aqueous solution is purified by dialysis until the electric conductivity is 10 μS or less, The aqueous solution was passed through a Whatman GF / F filter, and then the oven moisture at 60 ° C. was removed and solidified to obtain a metallic luster crystal of the exemplified compound. Yield 3.5g. The absorption maximum wavelength in a dilute aqueous solution (25 ° C.) was 523 nm. 538 ([M-4H] / 4), 716 in which one molecule of a side chain containing s-triazine was introduced and three molecules of 3-amino-1,2-propanediol were introduced with respect to one molecule of the dye from the MS spectrum. ([M-3H] / 3) and MS spectrum 904 in which two molecules of side chains containing s-triazine were introduced and two molecules of 3-amino-1,2-propanediol were introduced per molecule of the dye. [M-2] / 2) was observed.
^From the analysis of ¹ H NMR, an average of 1.5 molecules of side chains containing s-triazine are introduced per molecule of dye, and 2.5 molecules of 3-amino-1,2-propanediol are introduced. I was able to confirm.

  Other exemplary compounds can be synthesized in the same manner as described above by appropriately adjusting the side chain containing s-triazinyl, the type and content of the amine.

[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 NaOH 10 mol / L, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.22 μm to prepare a magenta ink liquid.

Composition of ink liquid A:
Dye (Exemplary Compound 1, l = 0, n = 1.5, m = 2.5) 3.50 g
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Orphin E 1010 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.9g

  Except for changing the coloring matter as shown in Table 4 below, ink liquids B to E and ink liquids F to H were used as ink liquids for comparison using the following compounds in the same manner as the preparation of ink liquid A. It was adjusted.

(Image recording and evaluation)
The following evaluation was performed on the ink jet inks of the above Examples (Ink Liquids A to E) and Comparative Examples (Ink Liquids F to H). The results are shown in Table 4.
In Table 4, the ozone resistance, moisture resistance, and printing density are as follows. For each ink-jet ink, photo glossy paper (EPSON photo paper <gloss>) is used with an ink jet printer (EPSON Co., Ltd .; PM-700C). (KA420PSK, EPSON) Evaluation after recording an image.

<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 this was used to put the image 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 5 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.

<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 print density at a print density of 100% is measured using a reflection densitometer (X-Rite 310TR), and when the print density is 2.2 or more, A, when 2.0 or less and less than 2.2, B, 2.0. When the value was less than C, the print density was evaluated in three stages.

  As is apparent from the results in Table 4, the inks of the examples using the dyes of the present invention have excellent ozone resistance, moisture resistance, and print density performance, and are extremely different from the other comparative examples. It can be seen that it has high performance.

[Example 2] Preparation and evaluation of color toner <Preparation of color toner>
3 parts by mass of the azo dye of the present invention (Exemplary Compound (1) m = 3, n = 1), resin for toner [styrene-acrylic acid ester copolymer; Hymer TB-1000F (trade name, manufactured by Sanyo Chemical Co., Ltd.) )] 100 parts by mass were mixed and pulverized by a ball mill, heated to 150 ° C. for melt-mixing, cooled, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type pulverizer. Further, classification was performed to select particles having a size of 1 to 20 μm to obtain toner.

<Evaluation>
To 10 parts by mass of this toner, 900 parts by mass of carrier iron powder (EFV250 / 400, trade name, manufactured by Nippon Iron Powder Co., Ltd.) was uniformly mixed to obtain a developer. When this developer is used for copying with a dry plain paper electrophotographic copying machine (NP-5000, trade name, manufactured by Canon Inc.), it has excellent spectral characteristics and exhibits excellent properties as a toner. I understood.

[Example 3]: Production and evaluation of color filter <Production of color filter>
(Preparation of positive resist composition)
Using 3.4 parts by mass of a cresol novolak resin (polystyrene-converted mass average molecular weight 4300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5), a phenol compound of the following formula O-naphthoquinonediazide-5-sulfonic acid ester (average of two hydroxyl groups esterified) 1.8 parts by mass, hexamethoxymethylolated melamine 0.8 parts by mass, ethyl lactate 20 parts by mass, and A positive resist composition was obtained by mixing 1 part by mass of the exemplary compound (1) (l = 0, m = 2.5, n = 1.5).

(Production of color filter)
The obtained positive resist composition was spin-coated on a silicon wafer, and then the solvent was evaporated. Next, the silicon wafer was exposed through a mask to decompose the quinonediazide compound. Thereafter, heating was performed at 100 ° C., and then the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. After the entire surface was exposed, it was heated at 150 ° C. for 15 minutes to obtain a magenta complementary color filter. The exposure was performed using an i-line exposure stepper HITACHI LD-5010-i (trade name, manufactured by Hitachi, Ltd., NA = 0.40). The developer used was SOPD or SOPD-B (both trade names, manufactured by Sumitomo Chemical Co., Ltd.).

<Evaluation>
FIG. 1 shows a transmission spectrum of the color filter obtained (measured using UV3100 manufactured by Shimadzu Corporation).

Claims (9)

The coloring composition containing the compound represented by General formula (1).

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. R ⁰ and R ¹ may be bonded to each other to form a ring.
L represents a single bond or a divalent linking group.
D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2).
n represents an integer of 1 or more. However, when n represents an integer of 2 or more, plural R ⁰ to R ^3, and L may each be the same or different.
In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ₁₄ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom. 2. The colored composition according to claim 1, wherein R ¹³ in the general formula (2) is a hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. In the general formula (2), R ¹⁶ is a hydrogen atom, and R ¹⁴ , R ¹⁵ , and R ¹⁷ are substituted or unsubstituted aryl groups or substituted or unsubstituted heterocyclic groups. The coloring composition as described in 2. In the general formula (1), D is the formula ^(2), compounds represented by a hydrogen atom from R 14 ^{to R 17} represents an n number removed residues, in any one of claims 1 to 3 The coloring composition as described.   Ink for inkjet recording containing the coloring composition of any one of Claims 1-4.   An ink jet recording method for forming an image using the colored composition according to claim 1 or the ink for ink jet recording according to claim 5.   The color filter containing the compound represented by General formula (1) of any one of Claims 1-4.   A color toner containing the compound represented by the general formula (1) according to any one of claims 1 to 4. The compound represented by General formula (1).

In general formula (1), R ^{0 to} R ³ each independently represents a hydrogen atom or a substituent. R ⁰ and R ¹ may be bonded to each other to form a ring.
L represents a single bond or a divalent linking group.
D represents a residue obtained by removing n hydrogen atoms from the compound represented by the general formula (2).
n represents an integer of 1 or more. However, when n represents an integer of 2 or more, plural R ⁰ to R ^3, and L may each be the same or different.
In General Formula (2), R ¹¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, or an acyl group. Each substituent may be further substituted.
R ¹² represents a hydrogen atom, a halogen atom, or a cyano group.
R ¹³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted.
R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, heterocyclic group, sulfonyl group, acyl group, carboxyl group, A sulfo group or a carbamoyl group is represented. Each substituent may be further substituted. However, R ¹⁴ and R ¹⁵ are not both hydrogen atoms, and R ¹⁶ and R ¹⁷ are not both hydrogen atoms.
Each of A ¹ and A ² is a carbon atom that may be substituted, or one of them is a carbon atom that may be substituted, and the other is a nitrogen atom.

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